Polymer Electrolytes for All-Solid-State Lithium Batteries Materials, Mechanisms, and Manufacturing

Polymer Electrolytes for All-Solid-State Lithium Batteries Materials, Mechanisms, and Manufacturing | Authorea try { document.documentElement.classList.add('js'); } catch (e) { } var _gaq = _gaq || []; _gaq.push(['_setAccount', 'G-8VDV14Y67G']); _gaq.push(['_trackPageview']); (function() { var ga = document.createElement('script'); ga.type = 'text/javascript'; ga.async = true; ga.src = ('https:' == document.location.protocol ? 'https://ssl' : 'http://www') + '.google-analytics.com/ga.js'; var s = document.getElementsByTagName('script')[0]; s.parentNode.insertBefore(ga, s); })(); Skip to main content Preprints Collections Wiley Open Research IET Open Research Ecological Society of Japan All Collections About About Authorea FAQs Contact Us Quick Search anywhere Search for preprint articles, keywords, etc. Search Search ADVANCED SEARCH SCROLL This is a preprint and has not been peer reviewed. Data may be preliminary. 11 April 2025 V1 Latest version Share on Polymer Electrolytes for All-Solid-State Lithium Batteries Materials, Mechanisms, and Manufacturing Author : ESRA KILAVUZ 0000-0001-9324-5346 [email protected] Authors Info & Affiliations https://doi.org/10.22541/au.174438746.62508292/v1 Published ChemistrySelect Version of record Peer review timeline 783 views 222 downloads Contents Abstract Information & Authors Metrics & Citations View Options References Figures Tables Media Share Abstract The growing demand for high-performance, safe, and sustainable energy storage systems has spurred significant interest in advanced lithium-ion batteries (LIBs). While conventional liquid electrolytes have enabled commercial success, their flammability, leakage risk, and poor electrochemical stability continue to pose critical limitations. Solid-state electrolytes offer a compelling alternative, with solid organic electrolytes (SOEs) emerging as particularly promising due to their lightweight nature, mechanical flexibility, and chemical tunability. This review presents a comprehensive analysis of recent developments in SOEs for LIBs, with a focus on solid polymer electrolytes (SPEs) and single-ion conducting polymer electrolytes (SICPEs). We highlight key advances in polymer matrix design, the role of functional fillers, and the influence of anionic group chemistry—such as carboxylate, sulfonate, and sulfonylimide moieties—on ionic conductivity and transport mechanisms. In addition, we evaluate state-of-the-art fabrication techniques, including solution casting, in situ polymerization, phase inversion, and electrospinning, that are critical to achieving scalable and robust electrolyte membranes. By comparing organic and hybrid organic–inorganic strategies, this review outlines current challenges and future directions for SOE development aimed at realizing safe, efficient, and high-energy-density LIBs. Article category: (Review) Subcategory: (Solid Polymer Electrolytes (SPEs), Lithium Ion Batteries, Single-Ion Conducting Polymer Electrolytes (SICPEs), Solid state Batteries) Title ((Polymer Electrolytes for All-Solid-State Lithium Batteries Materials, Mechanisms, and Manufacturing)) Author(s), and Corresponding Author(s)* (Esra KILAVUZ) ((Optional Dedication)) E. K. Author 1, Dr. Address line 1, Nigde Omer Halisdemir University, Central Research Laboratory,Central Campus, Bor Road, Nigde, 51240 / Turkiye E-mail: ( [email protected] ) Keywords: (( polymer membranes, lithium ion batteries, solid organic electrolytes, solid state batteries )) ((Abstract text. The growing demand for high-performance, safe, and sustainable energy storage systems has spurred significant interest in advanced lithium-ion batteries (LIBs). While conventional liquid electrolytes have enabled commercial success, their flammability, leakage risk, and poor electrochemical stability continue to pose critical limitations. Solid-state electrolytes offer a compelling alternative, with solid organic electrolytes (SOEs) emerging as particularly promising due to their lightweight nature, mechanical flexibility, and chemical tunability. This review presents a comprehensive analysis of recent developments in SOEs for LIBs, with a focus on solid polymer electrolytes (SPEs) and single-ion conducting polymer electrolytes (SICPEs). We highlight key advances in polymer matrix design, the role of functional fillers, and the influence of anionic group chemistry—such as carboxylate, sulfonate, and sulfonylimide moieties—on ionic conductivity and transport mechanisms. In addition, we evaluate state-of-the-art fabrication techniques, including solution casting, in situ polymerization, phase inversion, and electrospinning, that are critical to achieving scalable and robust electrolyte membranes. By comparing organic and hybrid organic–inorganic strategies, this review outlines current challenges and future directions for SOE development aimed at realizing safe, efficient, and high-energy-density LIBs.)) Introduction Considering the global push to reduce carbon emissions and the decreasing supply of fossil fuels, there is a pressing requirement to create energy conversion and storage technologies that are both efficient and eco-friendly. As we move into an age where energy needs to be smart and ubiquitous, lithium metal batteries (LMBs), which consist of lithium metal electrodes and solid electrolytes, are emerging as a strong contender for the future of battery technology due to their high energy capacity and safety features. Lithium-ion batteries (LIBs), known for their minimal memory effect, high energy density, and low self-discharge rates, have been on the market since 1991 and have seen widespread use in electric vehicles, wearable technology, and smart power grids [1,2] . Battery energy storage is recognized for its efficiency and dependability. In the charging phase, electrical energy accumulates at the anode and transforms into chemical energy at the cathode. On the contrary, when discharging, this stored energy is converted back into electrical form for use. This cycle of energy conversion underpins the reliable operation of batteries in storing and releasing power as needed. Electrolytes serve a crucial role in batteries, functioning as the conduit for ion transfer between electrodes, which in turn contributes to the battery’s improved performance and stability [3] . The energy density of a battery is characterized by its cell voltage and capacity, whereas its energy efficiency is reflected in its coulombic efficiency and cyclic stability [4] . Understanding these parameters is essential for evaluating the overall performance of batteries, as indicated in several studies [5–8] . Electrolytes, a crucial component of LIBs, are instrumental in the movement of lithium ions. The prevalent liquid electrolytes are made up of lithium salt molecules and organic solvents that dissolve these salts [9] . The interface where these liquid electrolytes meet the electrode material forms a solid-liquid junction, which is key in reducing interfacial impedance, while their superior ionic conductivity is vital for the batteries’ longevity and consistent performance [10] . The development of lithium metal batteries (LMBs) faces several challenges that impede their practical application. One of the primary issues is the ”shuttle effect” of lithium polysulfides, which affects the electrochemical performance and limits the battery’s efficiency [11] . Additionally, LMBs undergo substantial volume changes throughout charge-discharge cycles, make way for mechanical stress and potential failure [12] . The low conductivity of sulfur and its derivatives also presents a hurdle, as does the self-discharge phenomenon [5,13,14] . Another major concern is the uncontrolled growth of lithium dendrites, which can lead to short circuits and safety hazards [4,15] . The liquid electrolytes currently used in LMBs, typically composed of lithium salts and organic solvents, pose challenges such as poor cycling stability and interfacial instability, which further limit the batteries’ applicability [16,17] . Addressing these issues is crucial for advancing LMB technology and ensuring its role in the future of energy storage. The challenges faced by electrolyte systems in lithium-ion batteries (LIBs) highlight the crucial need to optimize several key functions: Ionic Conductivity: Electrolytes enable the movement of lithium ions from the anode, typically composed of graphite, to the cathode, often made of metal oxide. This process of ionic conduction is crucial for the battery’s functionality. Stability and Safety: The composition of electrolytes is vital for maintaining stability during the charging and discharging processes, as well as under varying temperature conditions. A stable electrolyte minimizes the risk of short circuits and prevents thermal runaway, thus enhancing the safety of the battery. Formation of Solid Electrolyte Interphase (SEI): The SEI layer, which forms on the surface of the anode, plays a protective role by preventing further reactions between the anode and the electrolyte. A well-developed SEI layer is critical for prolonging the battery’s lifespan. Voltage Window: Electrolytes also define the operational voltage range of a battery. High-voltage electrolytes can increase the energy density of the battery but require precise design to prevent degradation and ensure long-term performance. Liquid electrolytes are commonly employed in most lithium-ion batteries. They generally comprise a solution of solvents, salts, and various additives. Typical liquid electrolytes include compounds such as LiPF₆, LiBF₄, or LiClO₄ dissolved in organic solvents [18] . These electrolytes are widely used due to their excelent ionic conductivity and compatibility with established battery designs. Electrolytes can indeed be classified based on their physical states, which is a fundamental aspect of understanding their properties and applications as in Table 1 . Table 1 . Some of the most commonly used electrolytes for Li-Ion Batteries Yet, traditional Li-ion batteries consist of porous electrodes and liquid electrolytes and are therefore apt to degradation and serious safety issues. [19] . All solid state batteries (ASB) are a good alternative in this context, as these battery systems are generally based on solid electrolytes that combine better thermal and electrochemical stability and prevent dangerous electrolyte leakage compared to their liquid counterparts. [20] . The search for alternatives to liquid electrolyte systems is driven by the need to overcome challenges such as flammability, limited cyclability, and dendrite formation, which can compromise safety and performance [21] .Recent advances have introduced solid ceramic electrolytes, such as lithium metal oxides, as an alternative to traditional liquid electrolytes [22] . These solid electrolytes offer several advantages, including improved safety due to their reduced susceptibility to leakage and thermal runaway. Additionally, they exhibit high voltage stability, enabling operation at higher voltages without decomposition, and enhanced cycle life by minimizing side reactions and extending battery longevity [16,23] . The ongoing advancements in cell design have driven the demand for more efficient electrolytes, which are essential for enhancing the performance of Lithium-Ion Batteries (LIBs). Consequently, a diverse range of electrolytes has been developed, encompassing liquid, solid, aqueous, organic, and polymer-based options. The following section will explore some of the most prevalent electrolytes utilized in this field. Table 2 presents a comparative analysis of the benefits and drawbacks associated with liquid and solid electrolytes [24] . Table 2 . Properties of Different Types of Electrolytes High ionic conductivity Low ionic conductivity High stability in contact with lithium metal Broad stable electrochemical voltage window Superb mechanical properties Broad electrochemical window Formation of SEI layer in contact with electrodes High interface resistance High ionic conductivity at >100 °C Highly reactive Nonvolatility Unfavorable contact with electrodes Flammable Low toxicity Weak mechanical properties Solid Electrolytes Liquid electrolytes (LEs), commonly composed of lithium salts and organic solvents, are essential for dissolving lithium ions [25,26] . The ”solid-liquid” interface between LEs and the electrode material plays a crucial role in reducing interfacial impedance, thereby ensuring the longevity of lithium-ion batteries (LIBs) [27] . However, the decomposition of lithium salts at high temperatures, combined with the flammability and potential leakage of organic solvents, not to mention the low ion selectivity, present significant safety concerns. These issues have been linked to hazardous incidents, such as the explosion of Samsung cell phones and the spontaneous combustion of electric vehicles. In response, solid-state electrolytes (SSEs) have garnered considerable interest for their potential to enhance battery safety. Beyond ionic conductivity, several critical factors must be considered when developing electrolytes for solid-state LIBs. These include the stability of the lithium metal anode, the electrochemical compatibility with the cathode, the lithium-ion transference number, and the prevention of dendritic growth [7,28–30] . Utilizing solid-state high-voltage LIBs has achieved a retention capacity of 90% without compromising the electrochemical window [9,14] . Solid electrolytes (SEs) offer a safer and more robust alternative to aqueous electrolytes, which are prone to leakage and stability problems. Moreover, SEs reduce side reactions associated with high-voltage cathodes and lithium anodes, facilitating the advancement of micro LIBs that boast enhanced energy density and power capacity [31,32] . SSEs are typically categorized into two main categories, namely inorganic solid-state electrolytes (ISEs) and solid polymer electrolytes (SPEs). Solid-state lithium-ion batteries (LIBs) require the highest ionic conductivity, a broad electrochemical window, and superior electrochemical properties. Solid electrolytes can be divided into two main classes: organic and inorganic. Organic solid electrolytes are largely based on polymer composites, while inorganic ones are based on superionic conductive forms of lithium salt, perovskite type and different ceramic materials such as garnet. [5,33] . Organic polymer electrolytes continue to be marked by their low ionic conductivity, while their inorganic counterparts suffer from inadequate mechanical stability, presenting challenges for incorporation into mass battery production 2.1. Organic Solid Electrolytes Organic solid electrolytes are a type of solid-state electrolyte composed of organic materials, which are used primarily in energy storage and conversion devices like solid-state batteries. These electrolytes offer advantages such as flexibility, lightweight properties, and the potential for scalable production. Here’s a detailed breakdown of the subclassification of organic solid electrolytes in Table 3 [34,35] : Table 3 . The Subclassification of Organic Solid Electrolytes Solid polymer electrolytes (SPEs) are extensively researched due to their significant potential and adaptability. They are primarily composed of a polymer base integrated with various fillers such as ceramics, lithium salts, or ionic liquids [29,36] . These fillers are essential for enhancing certain properties of SPEs, particularly to boost ionic conductivity [36] . Additionally, the integration of fillers bolsters thermal and mechanical characteristics, ensuring the SPE maintains adequate flexibility and thermal resilience during the operation of batteries [26,37] . It’s important to highlight that adding fillers often lowers the polymer’s crystallinity, which in turn benefits ion movement and boosts ionic conductivity [20,26] . The ultimate aim is to develop SPEs that can supplant the electrolyte solutions currently used in most batteries, which have several limitations. The polymer bases most frequently utilized in SPEs include poly(ethylene oxide) (PEO), poly(vinylidene fluoride) (PVDF) and its copolymers, poly(ethylene glycol) (PEG), poly(acrylonitrile) (PAN), and poly(ethylene carbonate) (PEC). Fillers integrated into polymer matrices play crucial roles in enhancing the electrochemical performance of batteries, serving either active or passive functions [12,29] . Commonly utilized passive fillers include ceramics such as barium titanate (BaTiO 3 ), aluminum oxide (Al 2 O 3 ), silicon dioxide (SiO 2 ), and titanium dioxide (TiO 2 ), as well as carbon-based materials like graphite [17,22,38–42] . These substances are instrumental in bolstering mechanical integrity and thermal resilience. On the other hand, active fillers typically comprise ionic liquids like 1- ethyl - 3 - methyl imidazolium bis (tri fluoro methyl sulfonyl) imide (EMIM)(TFSI) and 1-butyl-3-methylimidazolium chloride (BMIM)(Cl), along with a variety of lithium salts including lithium tetra fluoro borate (LiBF 4 ), lithium hexa fluoro phosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), and lithium bis (tri fluoro methane sulfonyl) imide (LiTFSI) [26,39,41,43–45] . These active fillers are essential for augmenting the ionic conductivity of (SPEs), thereby improving both their inherent and thermal conductive properties. The selection of materials for SPE development is also influenced by the ion-dipole interactions within the polymer matrix, which facilitate the dissociation of lithium salts, thus enhancing the mobility and transfer number of lithium ions [23,46,47] . The primary specifications and features of SPEs are detailed in Table 4 [12,29,31,37] . Table 4. Fillers used in SPEs for LIBs Developed in Recent Years Na alginate, PEOY. Chen et al. 2021 LiTFSI Solution casting ∼10 - 4 (40 °C) [25] Cellulose triacetate, PEGMAKale et al. 2021 PYR14TFSI, LiTFSI Solution casting 5.24 × 10 –3 (25 °C) ∼0.43 Gum tragacanth [8] LiN Solution casting 8.28 × 10 –3 (25 °C) 0.989 PMMA, natural rubber [26] LiBF, LiI Solution casting 1.89 × 10 –6 (25 °C) 0.94–0.97 PEO [36] Chitosan-silica nanoparticles LiTFSI Solution casting 1.91 × 10 –4 (30 °C) 2.2. Polymer Electrolytes Typically, SPEs are synthesized by incorporating a lithium salt into a polymer matrix, which constitutes a dual-ion system. Within this system, both the anion and lithium ions (Li + ) are mobile [5] . However, the strong interaction between the Li + ions and the polymer matrix may impede the Li + migration, potentially reducing the transference number of Li + (tLi + ) to below 0.5 [41,48] . Furthermore, since the anions are inert during the electrode reaction, they tend to accumulate at the electrode/electrolyte interface, creating a concentration gradient [7,49,50] . This gradient can lead to cell polarization and significantly impair cell performance, manifesting as a voltage drop and increased resistance [5,17] . Polymer electrolytes stand out among various solid electrolyte options, drawing significant attention for their minimal volume change during charge/discharge cycles, their inherent safety features, and their manufacturability. These mercantile polymer electrolytes, when combined with lithium salts, function as dual-ion conductors where both the lithium cations and their corresponding anions are dynamic [7,47] . Typically, anions have a mobility rate that is fourfold that of lithium cations. This is because cation movement is closely linked with the Lewis acid sites within the polymer matrix, resulting in lithium cation migration accounting for merely a fifth of the total ionic current [51] . In the 1980s, Bannister and colleagues suggested the idea of a single lithium-ion conducting polymer electrolyte. This design anchors the anions within the polymer framework, allowing lithium ions to be the primary charge carriers. This innovative approach eliminates concentration gradients, potentially enabling rapid charge and discharge as predicted by Newman’s models [52,53] . In 1984, Ward et al. firstly announced two synthetic methods for which synthesis single ion conducting polymer electrolytes (SICPEs) [54] . Single-ion conducting polymer electrolytes are thus highly anticipated for future battery technologies, offering exceptional safety, accelerated charging, and superior energy storage capacity. The development of single-ion conducting polymers has witnessed significant advancements over the past three decades, as illustrated by the chronological progression from 1990 to 2020. In the 1990s, research focused on foundational polymer systems, including polyanionic polymers containing sulfonate and carboxylate groups, and copolymers incorporating oligo(oxyethylene) segments to enhance ion mobility. The 2000s marked the emergence of more sophisticated architectures such as fluorinated sulfonate ionomers (e.g., Nafion-Li), cross-linked networks, and polyphosphazenes with sulfonimide functionalities, which provided improved thermal and electrochemical stability. A notable expansion occurred in the 2010s with the introduction of polymer matrices featuring delocalized anions, lithium poly(perfluoroalkylsulfonyl)imide backbones, and ceramic-based star-shaped frameworks, all designed to enhance single-ion conductivity and mechanical integrity [55–57] . Furthermore, molecular designs employing click chemistry, hyperbranched structures, and covalent organic frameworks demonstrated a growing emphasis on structure-property optimization. The most recent developments in the 2020s have focused on integrating nanocomposite strategies, alternating block copolymers, and conjugated microporous frameworks, along with silica aerogel-based solid electrolytes. These innovations underscore the field’s shift toward multifunctional materials that combine high ionic conductivity with enhanced mechanical and chemical robustness, addressing critical challenges in next-generation solid-state battery technologies (Figure 1.) . In the subsequent section, a comprehensive examination of the structural arrangements of SIC polymers is presented. Following this, the focus will shift to an exploration of the various synthetic and fabrication techniques. Figure 1. A timetable of the development of single Li-ion SICPEs. In general, solid-state electrolytes (SSEs), which are classified as inorganic solid electrolytes (ISEs), solid polymer electrolytes (SPEs), and composite solid electrolytes (CSEs), have significant impact on battery performance. [55–57][7] 2.2.1. Anionic groups Ionic conductivity is closely linked to the charge and mobility of carriers, as well as the quantity of charge carriers. Enhancing the number of charge carriers and their migratory capabilities is crucial. For instance, by strategically designing the anion’s structure and placement (whether in the main or side chain), one can alter the anion-cation interaction [5,49] . This alteration aids in the cation’s dissociation, thereby boosting ionic conductivity. The essence of designing an anion structure lies in creating extensive conjugated systems or incorporating potent electron-withdrawing groups near the anion [52] . This strategy increases the spread of negative charges and reduces their attachment to cations, facilitating improved conductivity. Carboxylate (–CO2) anionic groups In 1984, Bannister et al. were the first to demonstrate single-ion conducting (SIC) polymer electrolytes by introducing perfluoroalkyl carboxylate groups (–(CF₂)₃CO₂) into poly(methyl methacrylate) (PMMA) (Figure 2.), achieving a high ionic conductivity of 2.5 × 10⁻⁶ S·cm⁻¹ at 60 °C. [36,54] . . Figure 2. Anionic groups in the SIC polymer backboneChemical structures of SIC polymer electrolytes: (a, b) carboxylate-based and (c–f) sulfonate-based. Black represents the polymer backbone, olive denotes the anion, and orange indicates the Li⁺ cation. [54] The synthesis of homopolymers is straightforward, yet disentangling their ionic conductivity from mechanical properties presents a challenge. To address this, a block copolymer was engineered, featuring a -CO 2 − anion and an oligo(oxyethylene) side chain as depicted in Figure 2a [5,9,54] . This copolymer was synthesized utilizing oligo-oxyethylene methacrylate and acrylamidocaproic acid as the monomers through a process of radical polymerization, as documented in reference [44] . Tsuchida and colleagues synthesized a similar SIC polymer that incorporated carboxylate anions (–CO 2 -) along with a side chain of oligo(oxyethylene) (–(OCH 2 CH 2 )–), as shown in Figure 2b [46] . This side chain is less effective at withdrawing electrons compared to the perfluoroalkyl group [32] . The ionic conductivity of this correspondent polymer was recorded at 10 -8 S/cm at 60 °C, that is meaningfully lower than the SIC polymer developed by Banister and others [13,23] . This difference is presumably due to the increased propensity of Li + ions to separate from the carboxylate group near the perfluoroalkyl group [7,23] . Therefore, substituting the hydrocarbon alkyl group with a perfluoroalkyl group could be a promising strategy to enhance ionic conductivity [5,21] . Despite the integration of carboxylate anionic groups into various polymer matrices such as methyl siloxane terminated polyethylene oxide-co-polymethyl lithium propionate siloxane, poly(oligo-oxyethylene methacrylate-co-alkali metal acrylamidocaproate), polystyrene-b-poly(lithium methacrylate-co-oligoethylene glycol methacrylate), and hyperbranched poly(ethylene oxide) (PEO), aimed at structural modifications for higher ionic conductivity, the ionic movement through polymers containing carboxylate anionic groups remains restricted due to the strong attraction to Li + cations [54,58,59] Sulfonate (–SO 3 ) anionic groups While research on carboxylate groups for ion transport has been somewhat limited, sulfonate groups have demonstrated a significant affinity for alkali cations. This property has been instrumental in the development of Nafion membranes, which facilitate selective ion transport in aqueous solutions [30,39] . Sulfonate groups are particularly effective due to their higher dissociation rate with lithium ions (Li + ). In 1991, Zhang and colleagues introduced a novel SIC polymer, featuring alkylsulfonate anions integrated into the PMMA backbone, further advancing the field of ion transport technology [4,46] . Research indicates that the strategic design of anionic structures with effective charge delocalization is a key approach to achieving solid ionic conductive polymer electrolytes (SICPEs) with superior ionic conductivity. In 2017, Shao and colleagues developed a perfluorobenzyl sulfonate anion-modified BAB triblock copolymer electrolyte [4,60] . This electrolyte’s structure is denoted as ’A-B-A’, where ’A’ stands for PEO (polyethylene oxide) or a copolymer of ethylene oxide and propylene oxide, and ’B’ represents poly(lithium 2,3,5,6-tetrafluorostyrene-4-sulfonate) [61] . As illustrated in Figure 3e , this innovative material demonstrated a remarkable ionic conductivity, reaching 1.5 x 10 -5 S/cm at 60 °C [61] . Moreover, the design strategically places strong electron-withdrawing groups in immediate vicinity to the sulfonate groups, as opposed to positioning them between the sulfonate groups and the polymer chain, enhancing the material’s properties. The comprehensive findings suggest that the presence of sulfonate groups within the polymer matrix contributes significantly to its ability to attract and bind lithium ions (Li + ), facilitating ion conduction. This ion conduction capacity can be further improved by integrating groups that are capable of withdrawing electrons. Sulfonylimide anionic groups Sulfonylimide anionic groups are particularly noteworthy due to the existence of two potent electron- attractant groups attached to a nitrogen atom, which significantly increases the hydrogen’s acidity on the same atom [5,9,48] (–SO 2 N( - )SO 2 – ). This characteristic was first documented in scientific literature back in 1984. The inclusion of such anionic groups within a polymer matrix is beneficial as it reduces the dissociation energy with lithium ions (Li + ), owing to the anions’ ability to delocalize charge effectively. This facilitates ionic transport, enhancing the performance of solid ionic conductor (SIC) polymer electrolytes. Consequently, SIC polymer electrolytes incorporating various sulfonylimide anions have been extensively studied, as depicted in Figure 3 . Anionic groups such as sulfonylimide, with their extensive conjugated systems, are capable of broadening the distribution of negative charge, thereby reducing the strength of anion binding to lithium ions (Li + ). In contrast, sulfonate anionic groups exhibit a reduced affinity for Li + ions when compared to carboxylate groups. This characteristic contributes to the enhanced ionic conductivity of a SIC polymer electrolyte when combined with polyethylene oxide (PEO), reaching a conductivity of 1.8 x 10 -7 S/cm at ambient temperature [44] . This value is ten times higher than that of the analogous polymer developed by Tsuchida and colleagues. Figure 3. Chemical structures of sulfonylimide-substituted SIC polymer electrolytes (a–d). Black: polymer backbone; olive: sulfonylimide anion; orange: Li + cation [54] The integration of sulfonylimide anions within the polymer framework has markedly enhanced ion transport capabilities, marking a leap forward in the development of advanced SIC polymer electrolytes. Beyond fluorinated groups, the bis(benzene sulfonyl) imide anions are also extensively researched, attributed to the benzene rings’ ability to distribute charge effectively. Highlighting this research, in 2014, Rohan and colleagues engineered lithium poly(4-styrene sulfonyl (phenylsulfonyl) imide) (PSSPSILi), incorporating bis(sulfonyl)imide anions into polystyrene. This compound exhibited an ionic conductivity of up to 1.1 x 10 -3 S/cm at ambient temperature, facilitated by an organic solvent [62] . 3.Polymer matrice 3.1.PVDF (Polyvinylidene fluoride) based electrolyte PVDF Polyvinylidene fluoride (PVDF) electrolytes were first developed in the 1980s and have since been selected for lithium battery applications due to their desirable characteristics. The research conducted by Tsunemi and colleagues delved into how various plasticizers and lithium salts influence the properties of these electrolytes, contributing to the advancement of battery technology [20] . This work has been instrumental in enhancing the performance and reliability of lithium batteries. Then Tarascon et al. debuted Li-ion battery with a fluorinated polymer (PVDF-HFP) as battery separator in 1996 [20] . Research on PVDF-based electrolytes has seen a steady rise up to the 20th century, with gel electrolytes being the predominant focus. Historically, enhancement techniques largely relied on single inert inorganic fillers such as TiO 2 , SiO 2 , MgO, montmorillonite (MMT), Al 2 O 3 , and polymer blending with materials like PEO, PAN, PMMA, PE, and PVP [20,63] . However, these methods only marginally improved the properties of PVDF electrolytes. The landscape has shifted in recent years due to the advent of solid electrolytes, leading to the emergence of numerous innovative materials and techniques, as illustrated in Figure 4 . In their study, Goncalves and colleagues developed a solid polymer electrolyte (SPE) using a PVDF-HFP copolymer combined with lithium bis((trifluoromethyl)sulfonyl)azanide (LiTFSI), employing solvent casting in the absence of additional fillers [6] . They investigated how varying amounts of LiTFSI influenced the SPE’s physical attributes, including ionic conductivity. The findings indicated that the PVDF-based solid electrolyte contributed to the dissociation of lithium salts (Figure 4, Figure 5) . However, the system comprising solely of the polymer and lithium salt struggled to fulfill the ion transfer requirements of electrolytes, resulting in battery performance that was significantly lower than that achieved with organic liquid electrolytes. Consequently, it is essential to explore alternative methods to improve the solid electrolytes’ performance, particularly in terms of ionic conductivity. Figure 4 . PVDF-based electrolytes exhibit several superior qualities when contrasted with PEO and Celgard counterparts [20] . Figure 5. Development of PVDF-based polymer electrolytes for lithiumbatteries Copyright (2019) American Chemical Society. Copyright (2020) Elsevier. Copyright (2017) American Chemical Society. Copyright (2017) Wiley. Copyright (2019) American Chemical Society. Copyright (2019) Elsevier. Copyright (2018) Wiley. Copyright (2019) American Chemical Society. Copyright (2019) American Chemical Society (Wu et al. 2022) 3.2.Poly(ethylene oxide) (PEO) based electrolytes Poly(ethylene oxide) (PEO) is a polyether compound with the monomer core H(OCH 2 CH 2 ) n OH. PEO is also known as polyethylene glycol (PEG) depending on the polymer chain length. PEO is synthesized by the cationic or anionic ring-opening reaction of ethylene oxide with the aid of a catalyst. Polyethylene oxide (PEO) is capable of forming complexes with lithium salts to produce polymer electrolytes. The ethylene oxide units within PEO exhibit a significant donor number for lithium ions, coupled with considerable chain flexibility, both of which are crucial for enhancing ion transport [64] . Moreover, PEO possesses a substantial dielectric constant and exhibits robust solvating capabilities for lithium ions. Consequently, solid polymer electrolytes (SPE) based on PEO have been the subject of extensive research (Figure 4). Nonetheless, it’s important to note that PEO is semi-crystalline in natüre [46] . It is the amorphous phase, particularly when the chain segments are activated above the glass transition temperature (T g ), that facilitates ion transport [36] . A diverse of methods have been utilized to enhance the ionic conductivity of polyethylene oxide (PEO)-based electrolytes. These include integrating plasticizers, incorporating nano-fillers, and blending polymers. Additionally, grafting short PEO oligomers onto the polymer backbone, cross-linking PEO-based polymers, and designing block copolymers with a PEO segment for conductivity, alongside other segments such as polystyrene (PS) and polyethylene (PE) for mechanical strength, are some of the innovative strategies adopted in this field [22,65–67] 4. Strategies for SPE Membrane Fabrication To incorporate SPE polymers into battery cells as solid-state electrolytes, they must be fabricated into membranes with sufficient mechanical strength to function effectively. A variety of fabrication technologies have been developed to produce high-performance membranes for seamless integration into full cells [68,69] . These methods aim to optimize the mechanical, thermal, and electrochemical properties of the membranes, ensuring their suitability for advanced battery applications. The development of PVDF- and PEO-based electrolytes, along with advancements in membrane fabrication techniques, continues to drive progress in the field of solid-state batteries [70] . By addressing the limitations of these polymer matrices and exploring innovative strategies for enhancing their performance, researchers are paving the way for the next generation of high-performance, safe, and efficient energy storage systems. 4.1.Casting A casting technique entails pouring a uniform solution—comprising SIC polymer electrolytes and a suitable solvent—onto an inert substrate, where it solidifies into a film.This technique is prevalent in membrane fabrication due to its affordability, wide applicability, and simplicity [23,26,39,45] . For example, Rolland and colleagues created a uniform solution by dissolving 10 wt% of (PS-b-P(OEGMA-co-MALi) in a 50:50 volume ratio of tetrahydrofuran/methanol, which was then cast onto Teflon films [29] . The solvent gradually evaporates, resulting in the formation of self-supporting membranes. with thicknesses between 300 micrometers to 1 micrometer, exhibiting an ionic conductivity of 2 x 10 -5 S/cm at ambient temperature [49] . It’s important to note that the rate of solvent evaporation significantly influences the quality and uniformity of the resulting SIC membranes. Thus, maintaining an ideal evaporation temperature and airflow is crucial. Occasionally, the casting process can be lengthy due to the gradual nature of the solvent evaporation. Additives such as aromatic polybenzimidazole (PBI), PVDF, and PVDF-HFP are occasionally incorporated to improve the mechanical robustness of membranes and facilitate their formation [5,7,54] . For instance, a self-supporting membrane can be fabricated by casting a blend of polymeric lithium tartaric acid borate (PLTB) with PVDF-HFP in a dimethylformamide (DMF) solvent [71,72] . This process not only strengthens the membrane but also contributes to its structural integrity during formation 4.2. Phase Inversion Phase separation techniques, in contrast to casting methods, are designed to create porous membranes that enhance plasticizer absorption through capillary action. These techniques are divided into three categories: nonsolvent-induced phase separation (NIPS), vapor-induced phase separation (VIPS), and liquid-extraction induced phase separation (LIPS) [5,45,46,54,61] . The NIPS method involves a solvent exchange that triggers phase separation. Initially, a homogeneous solution of SIC polymer is applied to a substrate. This substrate is then submerged in a nonsolvent bath, which extracts the solvent from the membrane [73,74] . Consequently, a dual-phase structure emerges within the membrane, comprising a polymer-rich phase (high in solvent) and a polymer-poor phase (low in solvent). Upon solvent removal, these regions solidify into a polymer matrix and pores, respectively. 4.3.In situ polymerization In situ polymerization is garnering significant interest for the creation of dense SIC polymer electrolytes. This method stands in contrast to traditional casting techniques, involving a homogeneous mixture of lithium salt monomers, photo-initiators or thermal initiators, and a solvent. The polymerization process is triggered by ultraviolet (UV) radiation or heat, applied to the solution spread on a sublayer, resulting in a concentrated SIC polymer membrane [50,59] . Notably, gel-type SIC polymer electrolyte membranes are adept at capturing more plasticizers through polymerization, resulting in improved compatibility with plasticizers through molecular-level blending which in turn increases ionic conductivity [75] . Moreover, in situ polymerization fosters an improved interface between electrolytes and electrodes when directly cast onto the electrodes, thereby reducing interfacial resistance and enhancing both the ionic conductivity and the stability of the electrolytes. 4.4. Electrospinning The electrospinning shows unique advantages in preparing thin membranes. Electrostatic spinning transforms a polymer solution into fine fibers, creating a non-woven fabric on the collector. These fibers are notable for their slender diameter and extensive surface area. The resulting film is highly porous, with small and evenly distributed pores, leading to superior absorbency even without modification. However, the mechanical strength of the film is compromised due to the plasticizing effect of the solvent, which is a significant drawback for its application in battery separator assembly, where robustness is crucial. Enhancing the mechanical properties of this film is therefore of paramount importance. Additionally, electrolyte membranes can be produced through a casting method, although this technique heavily relies on the specific mixture used [14,33,47] . The interaction of PVDF with other polymers or inorganic fillers reduces crystallinity, which is beneficial for increasing the rate of liquid absorption. 4.5. Polymeric composites method The method of creating polymeric composites involves the integration of various polymer materials through processes such as copolymerization, blending, or the introduction of initiators for cross-linking and grafting [26,46,65] . The primary goal is to diminish the polymer’s crystallinity, which is achieved by promoting interactions among polymers that increase spatial steric hindrance and disrupt the orderly movement of long polymer chains. This suppression of crystalline structure enhances the liquid absorbency and segmental motion, consequently improving ionic conductivity. For instance, Yesappa and colleagues utilized electron beam irradiation on PVDF-HFP electrolyte, leading to chain scission and crosslinking, which resulted in reduced crystallinity and heightened ionic conductivity [20] . Additionally, functional groups can be attached to the polymer backbone for specific purposes. PVDF-HFP materials, commonly synthesized by copolymerizing vinylidene fluoride and hexafluoropropylene, exhibit significantly lowered crystallinity. Similar outcomes are observed with blending and cross-linking techniques, which yield a uniform microporous structure in the electrolyte film. While cross-linking boosts ionic conductivity and mechanical strength, the presence of cross-linking agent residues can alter electrolyte properties. Therefore, the innovation of self-crosslinking electrolytes that leave no residues is considered highly promising for future applications. 5. Conclusion The pursuit of safer, high-performance, and sustainable lithium-ion batteries (LIBs) has driven considerable progress in the development of solid-state electrolytes, particularly organic-based systems. Solid polymer electrolytes (SPEs) and single-ion conducting polymer electrolytes (SICPEs) have emerged as promising candidates due to their inherent mechanical flexibility, structural tunability, and improved safety compared to conventional liquid electrolytes. This review has highlighted key advances in polymer matrix design, the influence of anionic group chemistry on ion transport, and the role of passive and active fillers in enhancing ionic conductivity and electrochemical stability. The evolution of SICPEs over the past three decades has demonstrated a clear trajectory toward materials with improved ion selectivity, higher transference numbers, and reduced dendrite formation. The introduction of sulfonate and sulfonylimide anions, along with block copolymer architectures and nanocomposite strategies, has significantly advanced the state-of-the-art. Meanwhile, fabrication techniques such as in situ polymerization, electrospinning, and phase inversion have enabled the production of mechanically robust, thin-film electrolyte membranes compatible with scalable battery manufacturing. Despite these achievements, challenges remain. Key issues such as achieving high ionic conductivity at ambient temperatures, improving interfacial compatibility with electrodes, and ensuring long-term electrochemical stability continue to limit commercial deployment. Future research should emphasize the design of multifunctional polymer systems that can simultaneously address these challenges through synergistic structural and compositional engineering. Overall, organic solid-state electrolytes represent a highly promising direction for next-generation lithium batteries. Continued innovation in material chemistry, processing technologies, and interface engineering will be critical to unlocking their full potential in safe, high-energy-density, and durable energy storage systems. Acknowledgment The authors gratefully acknowledge the financial support provided under the Wiley–TÜBİTAK Open Access Agreement. References [ 1] Shin J, Kim W, Yoo K, Kim H, Han M. Vehicular level battery modeling and its application to battery electric vehicle simulation. J Power Sources [Internet] 2023 ;556 (November 2022):232531. Available from: https://doi.org/10.1016/j.jpowsour.2022.232531[2] Praveen S, Santhoshkumar P, Joe YC, Senthil C, Lee CW. 3D-printed architecture of Li-ion batteries and its applications to smart wearable electronic devices. Appl Mater Today [Internet] 2020 ;20:100688. Available from: https://doi.org/10.1016/j.apmt.2020.100688[3] Xu J, Zhang J, Pollard TP, Li Q, Tan S, Hou S, et al. Electrolyte design for Li-ion batteries under extreme operating conditions. Nature 2023 ;614(7949):694–700. [4] Xu R, Cheng XB, Yan C, Zhang XQ, Xiao Y, Zhao CZ, et al. Artificial Interphases for Highly Stable Lithium Metal Anode. Matter [Internet] 2019 ;1(2):317–44. Available from: http://dx.doi.org/10.1016/j.matt.2019.05.016[5] Gao J, Wang C, Han DW, Shin DM. Single-ion conducting polymer electrolytes as a key jigsaw piece for next-generation battery applications. Chem Sci 2021 ;12(40):13248–72. [6] Barbosa JC, Gonçalves R, Costa CM, Lanceros-Méndez S. Toward Sustainable Solid Polymer Electrolytes for Lithium-Ion Batteries. ACS Omega 2022 ;7(17):14457–64. [7] Shan C, Wang Y, Liang M, Lu K, Xiong C, Hu W, et al. A comprehensive review of single ion-conducting polymer electrolytes as a key component of lithium metal batteries: From structural design to applications. Energy Storage Mater [Internet] 2023 ;63(September):102955. Available from: https://doi.org/10.1016/j.ensm.2023.102955[8] Yu X, Manthiram A. Sustainable Battery Materials for Next-Generation Electrical Energy Storage. Adv Energy Sustain Res 2021 ;2(5). [9] Zhou D, Shanmukaraj D, Tkacheva A, Armand M, Wang G. Polymer Electrolytes for Lithium-Based Batteries: Advances and Prospects. Chem [Internet] 2019 ;5(9):2326–52. Available from: https://doi.org/10.1016/j.chempr.2019.05.009[10] Ma S, Zhang D, Tang Z, Li W, Zhang Y, Zhang Y, et al. In Situ Polymerized Quasi-Solid Electrolytes Compounded with Ionic Liquid Empowering Long-Life Cycling of 4.45 V Lithium-Metal Battery. ACS Appl Mater Interfaces 2024 ;[11] Pan X, Yang P, Guo Y, Zhao K, Xi B, Lin F, et al. Electrochemical and Nanomechanical Properties of TiO2 Ceramic Filler Li-Ion Composite Gel Polymer Electrolytes for Li Metal Batteries. Adv Mater Interfaces 2021 ;8(16):48–50. [12] Vijayakumar V, Ghosh M, Asokan K, Sukumaran SB, Kurungot S, Mindemark J, et al. 2D Layered Nanomaterials as Fillers in Polymer Composite Electrolytes for Lithium Batteries. Adv. Energy Mater. 2023 ;13(15). [13] Guzmán-González G, Vauthier S, Alvarez-Tirado M, Cotte S, Castro L, Guéguen A, et al. Single-Ion Lithium Conducting Polymers with High Ionic Conductivity Based on Borate Pendant Groups. Angew Chemie - Int Ed 2022 ;61(7). [14] Kale SB, Nirmale TC, Khupse ND, Kale BB, Kulkarni M V., Pavitran S, et al. Cellulose-Derived Flame-Retardant Solid Polymer Electrolyte for Lithium-Ion Batteries. ACS Sustain Chem Eng 2021 ;9(4):1559–67. [15] Li Z, Yu R, Weng S, Zhang Q, Wang X, Guo X. Tailoring polymer electrolyte ionic conductivity for production of low- temperature operating quasi-all-solid-state lithium metal batteries. Nat Commun 2023 ;14(1). [16] Sun Y, Li G, Lai Y, Zeng D, Cheng H. High rate lithium-sulfur battery enabled by sandwiched single ion conducting polymer electrolyte. Sci Rep 2016 ;6. [17] Lee JH, Kang J, Kim SW, Halim W, Frey MW, Joo YL. Effective Suppression of the Polysulfide Shuttle Effect in Lithium-Sulfur Batteries by Implementing rGO-PEDOT:PSS-Coated Separators via Air-Controlled Electrospray. ACS Omega 2018 ;3(12):16465–71. [18] Hubble D, Brown DE, Zhao Y, Fang C, Lau J, McCloskey BD, et al. Liquid electrolyte development for low-temperature lithium-ion batteries. Energy Environ Sci 2022 ;15(2):550–78. [19] Chen M, Zhang J, Xia X, Qi M, Yin J, Chen Q. Self-supported Ni decorated NiO nanoflake arrays as promising cathode materials of hybrid batteries. Mater Res Bull [Internet] 2016 ;76:113–7. Available from: http://dx.doi.org/10.1016/j.materresbull.2015.12.005[20] Wu Y, Li Y, Wang Y, Liu Q, Chen Q, Chen M. Advances and prospects of PVDF based polymer electrolytes. J Energy Chem 2022 ;64:62–84. [21] Okazoe T, Watanabe K, Itoh M, Shirakawa D, Tatematsu S. 一种制备全氟化乙烯基醚单体的新途径：由非氟化化合物合成全氟化（烷氧基链烷酰基）氟化物. 2001 ;112:109–16. [22] Wimalaweera KK, Seneviratne VA, Dissanayake MAKL. Effect Of Al 2 O 3 Ceramic Filler On Thermal And Transport Properties Of Poly(Ethylene Oxide)-Lithium Perchlorate Solid Polymer Electrolyte. Procedia Eng [Internet] 2017 ;215(2017):109–14. Available from: https://doi.org/10.1016/j.proeng.2018.02.082[23] Kimura T, Matsumoto A, Inukai J, Miyatake K. Highly Anion Conductive Polymers: How Do Hexafluoroisopropylidene Groups Affect Membrane Properties and Alkaline Fuel Cell Performance? ACS Appl Energy Mater 2020 ;3(1):469–77. [24] Ko SJ, Kim MK, Bang JK, Seo CH, Luchian T, Park Y. Macropis fulvipes Venom component Macropin Exerts its Antibacterial and Anti-Biofilm Properties by Damaging the Plasma Membranes of Drug Resistant Bacteria. Sci Rep [Internet] 2017 ;7(1):1–14. Available from: http://dx.doi.org/10.1038/s41598-017-16784-6[25] Chen Y, Wang Y, Li Z, Wang D, Yuan H, Zhang H, et al. A flame retarded polymer-based composite solid electrolyte improved by natural polysaccharides. Compos Commun [Internet] 2021 ;26(April):100774. Available from: https://doi.org/10.1016/j.coco.2021.100774[26] Whba RAG, TianKhoon L, Su’ait MS, Rahman MYA, Ahmad A. Influence of binary lithium salts on 49% poly(methyl methacrylate) grafted natural rubber based solid polymer electrolytes. Arab J Chem [Internet] 2020 ;13(1):3351–61. Available from: https://doi.org/10.1016/j.arabjc.2018.11.009[27] Bekaert E, Buannic L, Lassi U, Llordés A, Salminen J. Electrolytes for Li- and Na-Ion Batteries: Concepts, Candidates, and the Role of Nanotechnology. Emerg Nanotechnologies Recharg Energy Storage Syst 2017 ;1–43. [28] Bai Y, Ma W, Dong W, Wu Y, Wang X, Huang F. In-Situ-Polymerized 1,3-Dioxolane Solid-State Electrolyte with Space-Confined Plasticizers for High-Voltage and Robust Li/LiCoO2 Batteries. ACS Appl Mater & Interfaces 2023 ;15(22):26834–42. [29] Sun Y, Zhan X, Hu J, Wang Y, Gao S, Shen Y, et al. Improving Ionic Conductivity with Bimodal-Sized Li 7 La 3 Zr 2 O 12 Fillers for Composite Polymer Electrolytes. ACS Appl Mater Interfaces 2019 ;11(13):12467–75. [30] Nicotera I, Simari C, Agostini M, Enotiadis A, Brutti S. A Novel Li+-Nafion-Sulfonated Graphene Oxide Membrane as Single Lithium-Ion Conducting Polymer Electrolyte for Lithium Batteries. J Phys Chem C 2019 ;[31] Kainat S, Anwer J, Hamid A, Gull N, Khan SM. Electrolytes in Lithium-Ion Batteries: Advancements in the Era of Twenties (2020’s). Mater Chem Phys [Internet] 2024 ;313 (November 2023):128796. Available from: https://doi.org/10.1016/j.matchemphys.2023.128796[32] Wang N, Chen X, Sun Q, Song Y, Xin T. Fast Li+ Transport Polyurethane-Based Single-Ion Conducting Polymer Electrolyte with Sulfonamide Side chains in the Hard Segment for Lithium Metal Batteries. ACS Appl Mater Interfaces 2023 ;15(33):39837–46. [33] Zhou Y, Wang X, Zhu H, Yoshizawa-Fujita M, Miyachi Y, Armand M, et al. Solid-State Lithium Conductors for Lithium Metal Batteries Based on Electrospun Nanofiber/Plastic Crystal Composites. ChemSusChem 2017 ;10(15):3135–45. [34] Wang Y, Zhai F, Zhou Q, Lv Z, Jian L, Han P, et al. Functional Applications of Polymer Electrolytes in High-Energy-Density Lithium Batteries. Macromol Chem Phys 2022 ;223(8):1–20. [35] Qu X, Guo Y, Liu X. Highly Stretchable and Elastic Polymer Electrolytes with High Ionic Conductivity and Li-Ion Transference Number for High-Rate Lithium Batteries. Chinese J Chem 2022 ;40(21):2559–67. [36] Li C, Huang Y, Chen C, Feng X, Zhang Z, Liu P. A high-performance solid electrolyte assisted with hybrid biomaterials for lithium metal batteries. J Colloid Interface Sci [Internet] 2022 ;608:313–21. Available from: https://doi.org/10.1016/j.jcis.2021.09.113[37] Li J, Li R, Li L xin, Yang H, Liu M quan, Xiang J, et al. A High-Filled Li7La3Zr2O12/Polypropylene Oxide Composite Solid Electrolyte with Improved Lithium-Ion Transport and Safety Performances for High-Voltage Li Batteries. ACS Appl Energy Mater 2022 ;5(9):10786–93. [38] Debelak B, Lafdi K. Use of exfoliated graphite filler to enhance polymer physical properties. Carbon N Y 2007 ;45(9):1727–34. [39] Teoh KH, Lim CS, Liew CW, Ramesh S. Preparation and performance analysis of barium titanate incorporated in corn starch-based polymer electrolytes for electric double layer capacitor application. J Appl Polym Sci 2016 ;133(14):1–8. [40] Aziz SB, Karim WO, Qadir KW, Zafar Q. Proton ion conducting solid polymer electrolytes based on chitosan incorporated with various amounts of barium titanate (BaTiO3). Int J Electrochem Sci [Internet] 2018 ;13(6):6112–25. Available from: https://doi.org/10.20964/2018.06.38[41] Sasikumar M, Krishna RH, Raja M, Therese HA, Balakrishnan NTM, Raghavan P, et al. Titanium dioxide nano-ceramic filler in solid polymer electrolytes: Strategy towards suppressed dendrite formation and enhanced electrochemical performance for safe lithium ion batteries. J Alloys Compd [Internet] 2021 ;882:160709. Available from: https://doi.org/10.1016/j.jallcom.2021.160709[42] Lin Y, Li X, Zheng W, Gang Y, Liu L, Cui X, et al. Effect of SiO2 microstructure on ionic transport behavior of self-healing composite electrolytes for sodium metal batteries. J Memb Sci [Internet] 2023 ;672(January):121442. Available from: https://doi.org/10.1016/j.memsci.2023.121442[43] McCallum R, Barghamadi M, Forsyth C, F. Hollenkamp A, Oldham G, J. Mahon P, et al. Comparing the Physicochemical, Electrochemical, and Structural Properties of Boronium versus Pyrrolidinium Cation-Based Ionic Liquids and Their Performance as Li-Ion Battery Electrolytes. J Phys Chem C 2021 ;125(15):8055–67. [44] Nguyen TKL, Lopez G, Iojoiu C, Bouchet R, Ameduri B. Novel single-ion conducting electrolytes based on vinylidene fluoride copolymer for lithium metal batteries. J Power Sources 2021 ;498(April). [45] Latifi M, Ahmad A, Hassan NH, Ben Youcef H, Kaddami H. Carboxymethyl chitin doped 1-butyl-3-methylimidazolium chloride based solid polymer electrolyte. Mater Today Proc [Internet] 2020 ;36:16–21. Available from: https://doi.org/10.1016/j.matpr.2020.04.745[46] Xue Z, He D, Xie X. Poly(ethylene oxide)-based electrolytes for lithium-ion batteries. J Mater Chem A 2015 ;3(38):19218–53. [47] Rohan R, Kuo TC, Chen MW, Lee JT. Nanofiber Single-Ion Conducting Electrolytes: An Approach for High-Performance Lithium Batteries at Ambient Temperature. ChemElectroChem 2017 ;4(9):2178–83. [48] Ahmed F, Choi I, Rahman MM, Jang H, Ryu T, Yoon S, et al. Remarkable Conductivity of a Self-Healing Single-Ion Conducting Polymer Electrolyte, Poly(ethylene-co-acrylic lithium (fluoro sulfonyl)imide), for All-Solid-State Li-Ion Batteries. ACS Appl Mater Interfaces 2019 ;11(38):34930–8. [49] Yip BRP, Javier Vázquez R, Jiang Y, McCuskey SR, Quek G, Ohayon D, et al. Conjugated Polyelectrolyte Thin Films for Pseudocapacitive Applications. Adv Mater 2024 ;36(1). [50] He Y, Wang C, Zou P, Lin R, Hu E, Xin HL. Anion-tethered Single Lithium-ion Conducting Polyelectrolytes through UV-induced Free Radical Polymerization for Improved Morphological Stability of Lithium Metal Anodes. Angew Chemie - Int Ed 2023 ;62(38). [51] Kanyo ZF, Christianson DW. Biological recognition of phosphate and sulfate. J Biol Chem [Internet] 1991 ;266(7):4264–8. Available from: http://dx.doi.org/10.1016/S0021-9258(20)64316-2[52] Gao J, Zhou J, Wang C, Ma X, Jiang K, Kim E, et al. Engineered networking in a family of solvent-free single-ion conducting borate network polymer electrolytes for Li-metal battery applications. Chem Eng J [Internet] 2022 ;450(P4):138407. Available from: https://doi.org/10.1016/j.cej.2022.138407[53] Ewing R, Hamidi S, Tian G, Proffitt D, Tonin S, Fregolent L. Testing Newman and Kenworthy’s Theory of Density and Automobile Dependence. J Plan Educ Res 2018 ;38(2):167–82. [54] Luo Y, Gao L, Kang W. A new review of single-ion conducting polymer electrolytes in the light of ion transport mechanisms. J Energy Chem [Internet] 2024 ;89:543–56. Available from: https://doi.org/10.1016/j.jechem.2023.11.005[55] Chen ZX, Zhao ZY, Lu P, Xiao XX, He S, Deng C, et al. Sulfonate-Group-Containing Polymeric Polyamide for Simultaneous Transparency and Flame Retardancy of Polycarbonate. ACS Appl Polym Mater 2023 ;5(7):4889–900. [56] Zhu Q, Liu Y, Shepard LB, Bhattacharya D, Sinnott SB, Reinhart WF, et al. Using Data-Science Approaches to Unravel Insights for Enhanced Transport of Lithium Ions in Single-Ion Conducting Polymer Electrolytes. Chem Mater 2024 ;[57] Gao J, Sun C, Xu L, Chen J, Wang C, Guo D, et al. Lithiated Nafion as polymer electrolyte for solid-state lithium sulfur batteries using carbon-sulfur composite cathode. J Power Sources [Internet] 2018 ;382(March):179–89. Available from: https://doi.org/10.1016/j.jpowsour.2018.01.063[58] Wang Q, Zhang H, Cui Z, Zhou Q, Shangguan X, Tian S, et al. Siloxane-based polymer electrolytes for solid-state lithium batteries. Energy Storage Mater [Internet] 2019 ;23(April):466–90. Available from: https://doi.org/10.1016/j.ensm.2019.04.016[59] Bergfelt A, Rubatat L, Brandell D, Bowden T. Poly(benzyl methacrylate)-poly[(oligo ethylene glycol) methyl ether methacrylate] triblock-copolymers as solid electrolyte for lithium batteries. Solid State Ionics [Internet] 2018 ;321(April):55–61. Available from: https://doi.org/10.1016/j.ssi.2018.04.006[60] Ren W, Cheng M, Wang Y, Zhang D, Yang Y, Yang J, et al. Boron–Based Electrolytes for Rechargeable Magnesium Batteries: Biography and Perspective. Batter. Supercaps 2022 ;5(9). [61] Shao Z, Jannasch P. Single lithium-ion conducting poly(tetrafluorostyrene sulfonate)-polyether block copolymer electrolytes. Polym Chem 2017; 8(4):785–94. [62] Rohan R, Sun Y, Cai W, Zhang Y, Pareek K, Xu G, et al. Functionalized polystyrene based single ion conducting gel polymer electrolyte for lithium batteries. Solid State Ionics [Internet] 2014 ;268(PB):294–9. Available from: http://dx.doi.org/10.1016/j.ssi.2014.10.013[63] Aziz SB, Woo TJ, Kadir MFZ, Ahmed HM. A conceptual review on polymer electrolytes and ion transport models. J Sci Adv Mater Devices [Internet] 2018 ;3(1):1–17. Available from: https://doi.org/10.1016/j.jsamd.2018.01.002[64] Appetecchi GB, Hassoun J, Scrosati B, Croce F, Cassel F, Salomon M. Hot-pressed, solvent-free, nanocomposite, PEO-based electrolyte membranes: II. All solid-state Li/LiFePO4 polymer batteries. J Power Sources 2003 ;124(1):246–53. [65] Gucci F, Grasso M, Shaw C, Leighton G, Marchante Rodriguez V, Brighton J. PEO-based polymer blend electrolyte for composite structural battery. Polym Technol Mater [Internet] 2023 ;62(8):1019–28. Available from: https://doi.org/10.1080/25740881.2023.2180391[66] Mindemark J, Lacey MJ, Bowden T, Brandell D. Beyond PEO—Alternative host materials for Li+-conducting solid polymer electrolytes. Prog Polym Sci [Internet] 2018 ;81:114–43. Available from: https://doi.org/10.1016/j.progpolymsci.2017.12.004[67] Zhao S, Wu Q, Ma W, Yang L. Polyethylene Oxide-Based Composites as Solid-State Polymer Electrolytes for Lithium Metal Batteries: A Mini Review. Front Chem 2020 ;8(August):1–7. [68] Junoh H, Jaafar J, Mohd Norddin MNA, Ismail AF, Othman MHD, Rahman MA, et al. A Review on the fabrication of electrospun polymer electrolyte membrane for direct methanol fuel cell. J Nanomater 2015 ;2015. [69] Kim AR, Vinothkannan M, Yoo DJ. Fabrication of Binary Sulfonated Poly Ether Sulfone and Sulfonated Polyvinylidene Fluoride-Co-Hexafluoro Propylene Blend Membrane as Efficient Electrolyte for Proton Exchange Membrane Fuel Cells. Bull Korean Chem Soc 2018 ;39(8):913–9. [70] Xiang Z, Bu F, Xing W, Na H, Zhang Y. Solvent induced fabrication of solid polymer electrolyte water electrolyzer: A study in sulfonated poly(ether ether ketone) based membrane electrode assembly. Fuel Cells 2015 ;15(1):246–50. [71] Meng N, Ye Y, Yang Z, Li H, Lian F. Developing Single-Ion Conductive Polymer Electrolytes for High-Energy-Density Solid State Batteries. Adv Funct Mater 2023 ;33(43). [72] Zhou Q, Zhang J, Cui G. Rigid–Flexible Coupling Polymer Electrolytes toward High-Energy Lithium Batteries. Macromol Mater Eng 2018 ;303(11):1–14. [73] Wang C, Quan X, Liao M, Li L, Zhou J. Computer Simulations on the Channel Membrane Formation by Nonsolvent Induced Phase Separation. Macromol Theory Simulations 2017 ;26(5):1–10. [74] Chang HH, Beltsios K, Lin DJ, Cheng LP. Formation of polyamide 12 membranes via thermal-nonsolvent induced phase separation. J Appl Polym Sci 2013 ;130(1):14–24. [75] Kuo DH, Lo R, Hsueh TH, Jan DJ, Su CH. LiSnOS/gel polymer hybrid electrolyte for the safer and performance-enhanced solid-state LiCoO2/Li lithium-ion battery. J Power Sources [Internet] 2019 ;429(May):89–96. Available from: https://doi.org/10.1016/j.jpowsour.2019.05.010 Esra Kilavuz received her Ph.D. in Chemistry from Nigde Omer Halisdemir University, Türkiye, focusing on conducting polymers and nanocomposites. She is currently a postdoctoral researcher at Drexel University’s Nanomaterials Institute, working on MXene-based energy storage systems. Her research interests include solid-state electrolytes, lithium-ion batteries, electrochemical materials, and polymer-based nanocomposites. She has published in peer-reviewed journals and presented at international conferences. Information & Authors Information Version history V1 Version 1 11 April 2025 Peer review timeline Published ChemistrySelect Version of Record 26 Sep 2025 Published Copyright This work is licensed under a Non Exclusive No Reuse License. Keywords lithium ion batteries polymer membranes solid organic electrolytes solid state batteries Authors Affiliations ESRA KILAVUZ 0000-0001-9324-5346 [email protected] Niğde Ömer Halisdemir University View all articles by this author Metrics & Citations Metrics Article Usage 783 views 222 downloads .FvxKWukQNSOunydq8rnd { width: 100px; } Citations Download citation ESRA KILAVUZ. Polymer Electrolytes for All-Solid-State Lithium Batteries Materials, Mechanisms, and Manufacturing. Authorea . 11 April 2025. DOI: https://doi.org/10.22541/au.174438746.62508292/v1 If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download. For more information or tips please see 'Downloading to a citation manager' in the Help menu . Format Please select one from the list RIS (ProCite, Reference Manager) EndNote BibTex Medlars RefWorks Direct import Tips for downloading citations document.getElementById('citMgrHelpLink').addEventListener('click', function() { popupHelp(this.href); return false; }); $(".js__slcInclude").on("change", function(e){ if ($(this).val() == 'refworks') $('#direct').prop("checked", false); $('#direct').prop("disabled", ($(this).val() == 'refworks')); }); View Options View options PDF View PDF Figures Tables Media Share Share Share article link Copy Link Copied! Copying failed. Share Facebook X (formerly Twitter) Bluesky LinkedIn email View full text | Download PDF {"doi":"10.22541/au.174438746.62508292/v1","type":"Article"} Now Reading: Share Figures Tables Close figure viewer Back to article Figure title goes here Change zoom level Go to figure location within the article Download figure Toggle share panel Toggle share panel Share Toggle information panel Toggle information panel Go to previous graphic Go to next graphic Go to previous table Go to next table All figures All tables View all material View all material xrefBack.goTo xrefBack.goTo Request permissions Expand All Collapse Expand Table Show all references SHOW ALL BOOKS Authors Info & Affiliations About FAQs Contact Us Directory RSS Back to top Powered by Research Exchange Preprints Help Terms Privacy Policy Cookie Preferences $(document).ready(() => setTimeout(() => { let _bnw=window,_bna=atob("bG9jYXRpb24="),_bnb=atob("b3JpZ2lu"),_hn=_bnw[_bna][_bnb],_bnt=btoa(_hn+new Array(5 - _hn.length % 4).join(" ")); $.get("/resource/lodash?t="+_bnt); },4000)); (function(){function c(){var b=a.contentDocument||a.contentWindow.document;if(b){var d=b.createElement('script');d.innerHTML="window.__CF$cv$params={r:'a004b83c5dbedf88',t:'MTc3OTU0NjIxOA=='};var a=document.createElement('script');a.src='/cdn-cgi/challenge-platform/scripts/jsd/main.js';document.getElementsByTagName('head')[0].appendChild(a);";b.getElementsByTagName('head')[0].appendChild(d)}}if(document.body){var a=document.createElement('iframe');a.height=1;a.width=1;a.style.position='absolute';a.style.top=0;a.style.left=0;a.style.border='none';a.style.visibility='hidden';document.body.appendChild(a);if('loading'!==document.readyState)c();else if(window.addEventListener)document.addEventListener('DOMContentLoaded',c);else{var e=document.onreadystatechange||function(){};document.onreadystatechange=function(b){e(b);'loading'!==document.readyState&&(document.onreadystatechange=e,c())}}}})();