Hybrid Solid Polymer Electrolytes Research Articles

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

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

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

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

Hybrid Solid Polymer Electrolytes Based on Epoxy Resins, Ionic Liquid, and Ceramic Nanoparticles for Structural Applications.

Solid polymer electrolytes (SPE) and composite polymer electrolytes (CPE) serve as crucial components in all-solid-state energy storage devices. Structural batteries and supercapacitors present a promising alternative for electric vehicles, integrating structural functionality with energy storage capability. However, despite their potential, these applications are hampered by various challenges, particularly in the realm of developing new solid polymer electrolytes that require more investigation. In this study, novel solid polymer electrolytes and composite polymer electrolytes were synthesized using epoxy resin blends, ionic liquid, lithium salt, and alumina nanoparticles and subsequently characterized. Among the formulations tested, the optimal system, designated as L70P30ILE40Li1MAl2 and containing 40 wt.% of ionic liquid and 5.7 wt.% of lithium salt, exhibited exceptional mechanical properties. It displayed a remarkable storage modulus of 1.2 GPa and reached ionic conductivities of 0.085 mS/cm at 60 °C. Furthermore, a proof-of-concept supercapacitor was fabricated, demonstrating the practical application of the developed electrolyte system.

A Supertough and Highly‐Conductive Nano‐Dipole Doped Composite Polymer Electrolyte with Hybrid Li+‐Solvation Microenvironment for Lithium Metal Batteries

AbstractAchieving solid polymer electrolytes with ceramic‐like fast single‐ion conduction behavior, separator‐required mechanical properties, and good lithium‐dendrite suppression capability is essential but extremely challenging for the practical success of solid‐state lithium‐metal batteries. The key to overcome this long‐standing bottleneck is to rationally design the Li+‐transport microenvironment inside the polymeric ion‐conductors. Herein, the concept of a nano‐dipole doped composite polymer electrolyte (NDCPE) is proposed using surface‐charged halloysite nanotubes (d‐HNTs) as the dopant to achieve a Li+‐transport‐friendly microenvironment in poly(vinylidene fluoride) (PVDF) based quasi‐solid electrolytes. Results show that the d‐HNTs doping can immobilize the anions and help dissociate the lithium salt, which leads to an advanced dynamic Li+‐interface yielding both a high Li+‐transference number (0.75 ± 0.04) and ionic conductivity (0.29 ± 0.04 mS cm−1 @R.T.). Moreover, compared with the commercial separator, the NDCPE thin‐film shows similar toughness, mechanical strength, and puncture resistance, but much superior capability for stabilizing the lithium‐metal anode. To understand the possible doping mechanism, a hybrid Li+‐solvation model combining the surface charges of the nanofiller, absorbed solvent molecules, and absorbed polymer chain unit is proposed and discussed for guiding the future studies on advanced hybrid solid polymer electrolytes.

Largely Promoted Mechano‐Electrochemical Coupling Properties of Solid Polymer Electrolytes by Introducing Hydrogen Bonds‐Rich Network

AbstractSolid polymer electrolytes (SPEs) and their composites are the most promising spices to access the commercial application in all‐solid‐state lithium batteries, where definite requirements for SPEs should be satisfied including moderate mechanical strength, high Li‐ion conductivity, and stable electrode/electrolyte interface. Herein, polyurethane‐based polymer (PNPU) is designed to further construct the hybrid solid polymer electrolyte (named as PNPU‐PVDF‐HFP) with poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) for high energy density solid‐state lithium metal batteries. The theoretical calculation and characterization demonstrate that PNPU‐PVDF‐HFP SPEs still maintain the multiple hydrogen bonding modes of PNPU, which contributes a significantly improved mechanical properties of the polymer membrane with compact structure. Moreover, it is corroborated that PNPU is involved to form the double Li+ transport paths in the hybrid electrolyte, accelerating the migration of lithium ions. Therefore, PNPU‐PVDF‐HFP SPEs are achieved with suitable tensile strength of 5.16 MPa and high elongation of 140.8%, high ambient ionic conductivity of 4.13 × 10−4 S cm−1, excellent ductile, and stability on the interface of lithium metal anode. The Li/ LiFePO4 and Li/Li[Ni0.8Co0.1Mn0.1]O2 solid‐state batteries using PNPU‐PVDF‐HFP SPEs present a stable cycling performance at 30 °C. This study provides a feasible strategy to achieve mechano‐electrochemical coupling stable SPEs for solid‐state batteries.

Enhanced Electrochemical Performance of Hybrid Solid Polymer Electrolytes Encompassing Viologen for All-Solid-State Lithium Polymer Batteries

Enhanced Electrochemical Performance of Hybrid Solid Polymer Electrolytes Encompassing Viologen for All-Solid-State Lithium Polymer Batteries

Interfacial chemistry and ion-transfer mechanism for a tailored poly(thioether)-enabled hybrid solid polymer electrolyte with electrochemical properties in all-solid-state lithium–sulfur batteries

The solid polymer electrolyte we are introducing benefited from the synergy between polyethylene oxide and oligomer poly(thioether) plasticizer, which exhibits enhanced electrochemical, mechanical tensile and good thermochemical properties.

A Flexible Sandwich‐Type Hybrid Solid Polymer Electrolyte Enables High‐Temperature of 80 °C Resistant Lithium Metal Solid‐State Batteries

The solid‐state electrolyte is a promising candidate for advancing the dual goals of high energy density and high safety for batteries. However, it is difficult for current solid electrolyte systems to balance the high ion transport, mechanical strength, thermal safety, and electrochemical stability simultaneously, which will greatly restrict their scale‐up and practical applications in batteries. Herein, a sandwich‐type hybrid solid polymer electrolytes (SHSPEs) is prepared via a simple coating method, the gel polymer filled in the middle porous polyethylene (PE) separator endows SHSPEs fast ion transport (7.13 × 10−4 S cm−1, 25 °C) and good mechanical properties (205.67 MPa), while the solid composite polymer layers on both sides ensure adequate lithium‐ion transfer number (0.42), electrochemical and thermal safety stability. The Li//Li symmetric battery with optimized solid electrolyte can circulate steadily for more than 1800 h, especially at 80 °C. For further illustration, the solid‐state LiFePO4//Li cells provide ideal cyclic stability and rate capability, as well as extreme temperature endurance till 80 °C. Thus, this work provides an auspicious strategy to design a safe, high‐strength, high‐energy density battery for high‐temperature special needs.

Facile in-Situ Polymerized Polymer Electrolytes in All Solid-State Lithium-Ion Batteries

With the push towards renewable energy sources and “green” technologies, lithium-ion batteries (LIBs) have proven to be necessary across multiple technological realms, the biggest of which is currently the electric vehicle (EV) and grid storage markets. But the popular choice of liquid organic electrolytes in LIBs suffers from safety concerns, which motivated significant innovations in safer solid-state electrolytes. Among them, solid polymer electrolytes (SPEs) have shown great potential due to their processability, flexibility and tunability of physical properties. The past decade has seen rapid evolution in the development of SPE LIBs, but most of them still stand inadequate. SPEs are typically processed either by using solvents, or by using them in their solid state, to blend with the active electrode materials. While these systems are often subject to additional compression to promote continuous electrolyte-electrode interface, they still suffer from the almost unavoidable formations of voids, and inhomogeneous contact between the active materials and the SPEs. Furthermore, most of these processes require excessive amounts of SPEs, and yet result in a large interfacial resistance.Here we introduce a novel one-step manufacturing strategy for polymer electrolytes in solvent-free SPE LIBs. The process involves in-situ polymerization of a liquid-monomer precursor directly infiltrated into a dry jelly roll or individual electrodes to form SPE cells. Our microscopy and FIB experiments confirmed a near-perfect polymer infiltration in porous cathodes, while electro-chemical tests confirmed excellent characteristics of cathode-electrolyte interfaces. The cycling performance of lithium iron phosphate (LFP) half cells using thus produced and infiltrated SPE showed very good stability and columbic efficiency. In addition to single-ion conductive SPEs, we tested hybrid SPE systems where Li salts were added into the single-ion conductive SPEs to improve rate and capacity utilization.

Development of a New Crosslinked Highly Conductive Hybrid Electrolyte based on Polyetherdiamine, Diphenylmethane Diisocyanate and Organosilanes for Efficient Lithium‐Metal Battery

AbstractIn this study, a new crosslinked organic‐inorganic hybrid polymer electrolyte membrane is developed by first reacting polyetherdiamine with diphenylmethane diisocyanate, followed by addition of organosilane precursors 3‐(glycidyloxypropyl) trimethoxysilane and 2‐[methoxy(polyethyleneoxy) propyl] trimethoxysilane and LiClO4 salt. Various characterization methods are employed to probe the crystallinity behavior, morphology, ionic interactions, thermal stability, architectural durability and dynamic performance of the hybrid solid polymer electrolyte (HSPE) membranes. Among the electrolytes, the HSPE membrane with [EO]/[Li] ratio of 32 delivers the excellent ionic conductivity value of 1.2×10−4 S cm−1 at 30 °C. When the hybrid membrane without salt is plasticized with various electrolyte solvents, the ionic conductivity enhances significantly to values in the range of 1.2 to 1.8×10−3 S cm−1 at 30 °C. The lithium metal battery (LMB) assembled with the gel polymer electrolyte (GPE), lithium anode and LiFePO4 cathode provides excellent rate and cycle performances. The LMB delivers very stable discharge capacity of 121.1 mAh g−1 after 150 cycles at the rate of 0.1 C with 97.6 % capacity holding compared to first cycle and exhibits above 99 % Coulombic efficiency values. The present crosslinked hybrid polymer electrolytes are potentially promising for the future development of high performance lithium‐metal batteries.

Lithium-Ion Battery Solid Electrolytes Based on Poly(vinylidene Fluoride)-Metal Thiocyanate Ionic Liquid Blends.

Solid polymer electrolytes (SPEs) are required to improve battery safety through the elimination of the liquid electrolyte solution in current batteries. This work is focused on the development of a hybrid SPE based on poly(vinylidene fluoride), PVDF, and 1-butyl-3-methylimidazolium cobalt(II) isothiocyanate, [BMIM]2[(SCN)4Co] magnetic ionic liquid (MIL), and its battery cycling behavior at room temperature. The addition of MIL in filler contents up to 40 wt % to the PVDF matrix does not influence the compact morphology of the samples obtained by solvent casting. The polar β-phase of PVDF increases with increasing MIL content, whereas the degree of crystallinity, thermal degradation temperature, and mechanical properties of the MIL/PVDF blends decrease with increasing MIL content. The ionic conductivity of the MIL/PVDF blends increases both with temperature and MIL content, showing the highest ionic conductivity of 7 × 10-4 mS cm-1 at room temperature for the MIL/PVDF blend with 40 wt % of MIL. The cathodic half-cells prepared with this blend as SPE show good reversibility and excellent cycling behavior at different C-rates, with a discharge capacity of 80 mAh g-1 at a C/10-rate with a Coulombic efficiency of 99%. The developed magnetic SPE, with excellent performance at room temperature, shows potential for the implementation of sustainable lithium-ion batteries, which can be further tuned by the application of an external magnetic field.

Long-chain fluorocarbon-driven hybrid solid polymer electrolyte for lithium metal batteries

A poly(DFMA-co-MMA)–SCN–LiTFSI hybrid solid polymer electrolyte and aPDDA-TFSI anode layer were developed for lithium metal batteries.

Metal organic framework optimized hybrid solid polymer electrolytes with a high lithium-ion transference number and excellent electrochemical stability

PEO-based SPEs were optimized using an NH2-MIL-125 MOF as an additive. Large pores in the MOF allow the passage of lithium ions, inhibit the movement of anions and greatly increase the lithium-ion transference number of batteries.

Enhanced interfacial kinetics and fast Na+ conduction of hybrid solid polymer electrolytes for all-solid-state batteries

All-solid-state batteries suffer from drastic interfacial reactions between the solid electrolyte and electrode, which restricts the performance of the full cell. Herein, a hybrid solid polymer electrolyte with high ionic conductivity and stability has been fabricated by in-situ polymerization of poly(ethylene glycol) diacrylate (PEGDA) on glass fiber matrix, followed by polyethylene glycol (PEG) infiltration. Such hybrid electrolyte, namely GF@PEGDA@PEG (GFPP), is featured with an interconnecting ionic conducting network and demonstrates high ionic conductivities of 0.8 × 10−4 S cm−1 at 20 °C and 4.5 × 10−3 S cm−1 at 60 °C. The ex-situ Attenuated Total Reflectance-Fourier Transform Infrared spectroscopy (ATR-FTIR) of Na/GFPP/Na symmetrical battery proves the excellent stability of GFPP. Furthermore, in-situ Electrochemical Impedance Spectroscopy (EIS) analysis and in-situ Raman spectra confirm the enhanced interfacial dynamics achieved by GFPP, being conducive to the intercalation/deintercalation of Na+. Meanwhile, the optical microscope and X-ray photoelectron spectroscopy (XPS) demonstrate the formation of a stable SEI film and limited interfacial side reaction by the incorporation of GFPP. Full sodium metal batteries based on GFPP have been assembled and demonstrated satisfactory electrochemical performance. After being tested for 1100 cycles at a rate of 0.3 C, the Coulombic efficiency of Na3V2(PO4)3 (NVP) /GFPP/Na full cell remains at almost 99%, with a capacity retention of 91.4%.

Design, fabrication and application of PEO/CMC-Li @PI hybrid polymer electrolyte membrane in all-solid-state lithium battery

A novel PEO/CMC-Li @PI hybrid solid polymer electrolyte membrane was designed/assembled by utilizing the polyethylene oxide (PEO) as matrix, the modified N-carboxymethyl chitosan (CMC-Li) as the facilitator to accelerate the transport of lithium ions and the as-prepared polyimide (PI) non-woven fabric as supporting framework. The CMC-Li was firstly synthesized and then combined with PEO and PI non-woven fabric to assemble PEO/CMC-Li@PI membrane using in all solid-state battery (ASSB). The microscopic morphology of the PEO/CMC-Li@PI hybrid membrane was characterized by SEM images. The membranes thermodynamic behaviors were analyzed by the DSC/TG curves, showing that the Tm of the PEO/CMC-Li@PI decreased to 46.8 °C. When assembled into all-solid-state battery, the PEO/CMC-Li@PI membrane demonstrated the high ionic conductivities of 3.16 × 10–5 S/cm (30 °C) and 3.15 × 10–4 S/cm (60 °C) calculated from EIS spectra. The electrochemical window of the PEO/CMC-Li@PI cell was measured up to ~5 V at 60 °C. Moreover, the cell with PEO/CMC-Li@PI also delivered excellent electrochemical performances by comparing with other membranes. The high discharge capacities and cycling stability in PEO/CMC-Li@PI cell were assigned to the enhanced ionic conductivity by the added CMC-Li derivative and the improved mechanical properties by the PI non-woven fabric skeleton. The fabrication strategy of the novel PEO/CMC-Li@PI membrane may provide some new design directions for the solid polymer electrolytes in all-solid-state battery.

Titanium dioxide nano-ceramic filler in solid polymer electrolytes: Strategy towards suppressed dendrite formation and enhanced electrochemical performance for safe lithium ion batteries

Solid polymer electrolytes (SPEs) in lithium-ion batteries (LIBs) are emerging as promising alternative for liquid electrolytes. However, one of the drawbacks of SPEs is incompatibility between lithium metal anode/electrolyte that leads to the low ionic conductivity and lower cycling performance of LIBs. The present study show that fabrication of free-standing flexible hybrid solid polymer electrolyte (HSPE) based on poly(vinylidene fluoride-co-hexafluoro propylene)/poly(vinyl acetate) polymer blend electrolyte with TiO2 nano-ceramic filler (NCF). The incorporation of TiO2-NCF aids in simultaneous improvements of the ionic conductivity and mechanical properties of host matrix. HSPE with 7.5 wt% TiO2 exhibits highest ionic conductivity of 2.69 × 10−3 S cm−1 at 30 °C, which is ~2.5 time higher than ceramic free HSPE. In addition, the incorporation of TiO2 enhances the high thermal stability (thermal degradation at 350 °C) and mechanical strength (stress 8.4 MPa) of the HSPE. Remarkably, HSPE with 7.5 wt% TiO2-NCF possess large Li+ transference number (0.53) with extended electrochemical stability window (5.4 V) and superior compatibility with lithium metal which is highly desirable for high voltage LIBs. The Li/HSPE/LiFePO4 cell showed superior charge discharge properties, cycling stability and rate capability. Suppression of growth and proliferation of Li dendrites was demonstrated by time dependent impendence analysis. Furthermore, density functional theory (DFT) calculations confirm the mutual interactions between TFSI− and ions in electrolytes and that between TiO2 segments and polymer segments. This work exemplifies the significant role of TiO2-NCF in enhanced electrochemical performance of polymer based free standing flexible HSPE.

Lithiated nanosheets hybridized solid polymer electrolyte to construct Li+ conduction highways for advanced all-solid-state lithium battery

Solid-state electrolyte is a key component of high-energy-density and security all-solid-state lithium metal battery. However, the present solid polymer electrolyte (SPE) often suffers from the trade-off between ionic conductivity and mechanical stability. To this end, lithiated polydopamine-modified graphene oxide nanosheets (LiDGO) are fabricated, and incorporated into the representative poly(ethylene oxide) (PEO) matrix to prepare hybrid solid polymer electrolyte (HSPE). Despite the decreased crystallinity of PEO, the intrinsic advantage of organic-inorganic hybridization affords PEO-based HSPE highly improved mechanical stability. The tensile strength and elongation at break of HSPE are, respectively, 237% and 133% higher than those of blank PEO. The constructed long-range conduction pathways with locally concentrated Li+ at PEO-LiDGO interfaces impart HSPE highly enhanced ionic conductivity. The ionic conductivity reaches 3.4 × 10−5 S cm−1 at 30 °C, 10 times higher than that of blank PEO. These then bring excellent battery performances. The assembled battery achieves a discharge capacity of ~156 mAh g−1 after 200 cycles with ultra-high capacity retention of 98.7%. The strategy of utilizing lithiated nanosheets to address the trade-off between ionic conductivity and mechanical stability of SPE may pave the way for the development of high performance all-solid-state lithium metal batteries.

Multiclaw-shaped octasilsesquioxanes functionalized ionic liquids toward organic-inorganic composite electrolytes for lithium-ion batteries

In this work, we have successfully synthesized a series of multiclaw-shaped octasilsesquioxanes functionalized ionic liquids and then used it developing novel hybrid solid polymer electrolytes (SPEs) with high room temperature ionic conductivity. The effect of POSS ionic liquids with varying chain in imidazole on the microstructures, thermal stabilities and electrochemical properties of the obtained SPEs were studied. The scanning electron microscope images of SPEs membranes confirm that the POSS ionic liquids were uniformly distributed in the polymer matrix. The solid polymer electrolytes exhibit high electrochemical stabilities with a wide electrochemical window up to 5.0 V, a lithium-ion transference number (tLi+) of 0.32 and high ionic conductivity of 3.06 × 10−4 S cm−1 at 22 °C. Moreover, the Li/LiFePO4 cells containing POSS-ILs-SPEs exhibit excellent cycling performance and rate capability, the initial discharge capacity is 150.7 mAh g−1 and initial coulombic efficiency is 100% at a rate of 0.1C. The capacity of the cells can reach to 130 mAh g−1 and the coulombic efficiency is 99.9% after 90 cycles.

Polycation ionic liquid tailored PEO-based solid polymer electrolytes for high temperature lithium metal batteries

Poly(ethylene oxide) (PEO)-based polymer electrolytes are promising candidates for solid-state electrolytes in safer, next generation lithium metal batteries. Despite their benefits however, PEO-based electrolyte exhibits highly crystalline ethylene oxide chains that provide poor ionic conductivity and, thus severely limit its practical application. Here, we report the use of hydroxypropyl trimethylammonium bis(trifluoromethane) sulfonimide chitosan salt (HACC-TFSI), which is an amorphous poly(ionic liquid) based biomass chitosan derivative, as a modifier for PEO-based solid polymer electrolytes (SPEs) to address these deficiencies. Hybrid SPEs with HACC-TFSI display enlarged amorphous regions with enhanced ionic conductivity. Interactions between quaternary ammonium cations and TFSI− anions in hybrid SPEs are also found to promote dissociation between Li+ and TFSI−, which further increases ionic mobility. Moreover, the electrochemical stability, mechanical strength, and thermal stability of hybrid SPEs are collectively superior to blank SPEs without HACC-TFSI. LiFePO4/SPEs/Li full-cells assembled using 10wt% HACC-TFSI in PEO (10%HACC-TFSI/SPEs) electrolyte provide a capacity of 161.3 mAh g−1 and operate with excellent cycle performances at 0.2 C and 60 °C. Even when the temperature is increased to 150 °C, LiFePO4/SPEs/Li cells with 10%HACC-TFSI/SPEs still display remarkable cycle performance with 73% capacity retention after 100 cycles at 1 C rate.

Functionalized cellulose as quasi single-ion conductors in polymer electrolyte for all-solid–state Li/Na and Li[sbnd]S batteries

Solid polymer electrolytes (SPEs) with new functionalized ethyl cellulose bearing a lithium/sodium fluorosulfonylimide group (Ethyl cellulose-LiFSI/NaFSI) is proposed as quasi single ion (Li+/Na+) conducting polymer electrolyte for all-solid-state lithium and sodium batteries. The degree of ethyl cellulose functionalization by anion of lithium and sodium salt measured by elemental analysis was 48 and 53%, respectively. The complex of Li(FSI-ethyl cellulose)/PEO exhibits a Li-ion transference number of TLi+ = 0.9, and a Na ion transference number of TNa+ = 0.6 for Na(FSI-ethyl cellulose),which are much higher than those reported for ambipolar LiFSI or NaFSI/PEO SPEs under the same measurement conditions. The generated SPEs showed a high electrochemical and mechanical stability as well as a practical ionic conductivity value of ~10−4 S·cm−1 at 80 °C. All solid-state lithium, sodium and Li/Sulfur cells cycled with quasi single ion conducting hybrid SPE exhibit reversible cycling and good performance at 70 °C, making them promising, environmentally benign and cost-effective candidates for use in advanced energy storage systems.