PEO-based Polymer Electrolytes Research Articles

Stabilization of the Interface between a PEO-Based Lithium Solid Polymer Electrolyte and a 4-Volt Class Cathode, LiCoO2, by the Addition of LiPF6 as a Lithium Salt

Stabilization of the Interface between a PEO-Based Lithium Solid Polymer Electrolyte and a 4-Volt Class Cathode, LiCoO2, by the Addition of LiPF6 as a Lithium Salt

Flexible High Lithium-Ion Conducting PEO-Based Solid Polymer Electrolyte with Liquid Plasticizers for High Performance Solid-State Lithium Batteries.

Lithium-ion secondary batteries (LIB) with high energy density have attracted much attention for electric vehicle (EV) applications. However, LIBs have a safety problem because these batteries contain a flammable organic electrolyte. As such, all-solid secondary batteries that are not flammable have been extensively reported recently. In this study, we have focused on polymer electrolytes, which is flexible and is expected to address the safety problem. However, the conventional polymer electrolytes have low electrial conductivity at room temperature. Various attempts have been made to solve this problem, such as the addition of inorganic fillers and ionic liquids; however, these composite polymer electrolytes have not yet reached a practical level of lithium-ion conductivity. In this study, high electrical conductivity and lithium dendrite formation-free PEO based composite electrolytes are developed with both a filler of Li6,4La3Zr1.4Ta0.6O12 and liquid plasticizers of tetraethylene glycol dimethyl ether and 1,2 dimethoxyethane. The proposed flexible polymer electrolyte shows a high electrical conduciviy of 6.01×10-4 S cm-1 at 25 °C.

Effect of hBN on Response Times of PEO-Based Electrochromic Devices

In this study, all solid state electrochromic devices (ECDs) without plasticizer such as propylene carbonate were fabricated by sol-gel spin coating method. WO3 nanoparticles and PEO based polymer electrolyte solutions with hBN and without hBN nanoparticles were prepared. These solutions were sol-gel spin- and dip-coated on ITO-glass, respectively. For determining the effect of hBN nanoparticles, four configuration of ECDs were fabricated. The fast bleaching and coloring times of fabricated ECDs were obtained with hBN nanoparticles in WO3 and PEO based polymer electrolyte thin films as 1.15 seconds. Glass/ITO/hBN-WO3/hBN-PEO-based-polymer electrolyte/ITO/Glass electrochromic device is turned on and off 60 times. After 60 cycle, the device coloring time changed to 2-3 seconds, bleaching times changed to 30 seconds.

Reinforced flexible solid-state electrolyte membrane by polyurethane polymer of intrinsic microporosity for high-energy-density lithium metal battery

Poly (ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) are restricted in commercial applications due to the low ionic conductivity at ambient temperature and fragile mechanical properties. Polyurethanes (PUs) are unique materials coupled with superior rigidity and flexibility. Herein, we designed a novel polyurethane polymer of intrinsic microporosity (PPU), which was incorporated with PEO-based polymer electrolyte to prepare composite polymer electrolyte (CPE). The physicochemical and electrochemical properties of CPE membranes were explored. The high ionic conductivity (1.82 × 10−3 S cm−1 at 50 °C) and superior interfacial stability with the lithium anode was obtained. Furthermore, the rate performances and the cycling properties of CPE in LiFePO4 (LFP) batteries were extensively studied. The CPE-15% PPU film showed the excellent electrochemical stability of 84.3% capacity retention after 890 cycles at 0.5 C and 82.4% capacity retention after 500 cycles at 1.0 C at 50 °C. Especially, the CPE matched with high-voltage LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode delivered long-term stable cycling performances. The novel polymer electrolyte acquired could open up a new horizon to achieve high stable lithium metal batteries.

Correlation between Ionic Conductivity and Mechanical Properties of Solid-like PEO-based Polymer Electrolyte.

Poly(ethylene glycol) methyl ether methacrylate polymer networks (PEO-based networks), with or without anionic bis(trifluoromethanesulfonyl)imide (TFSI)-grafted groups, are promising electrolytes for Li-metal all solid-state batteries. Nevertheless, there is a need to enhance our current understanding of the physicochemical characteristics of these polymer networks to meet the mechanical and ionic conductivity property requirements for Li battery electrolyte materials. To address this challenge, our goal is to investigate the impact of the cross-linking density of the PEO-based network and the ethylene oxide/lithium ratio on mechanical properties (such as glass transition temperature and storage modulus) and ionic conductivity. We have synthesized a series of cross-linked PEO-based polymers (si-SPE for single ion solid polymer electrolyte) via solvent-free radical copolymerization. These polymers are synthesized by using commercially available lithium 3-[(trifluoromethane)sulfonamidosulfonyl]propyl methacrylate (LiMTFSI), poly(ethylene glycol)methyl ether methacrylate (PEGM), and [poly(ethylene glycol) dimethacrylate] (PEGDM). In addition, we have synthesized a series of cross-linked PEO-based polymers (SPE for solid polymer electrolyte) using LiTFSI as the ionic species. Most of the resulting polymer films are amorphous, self-standing, flexible, homogeneous, and thermally stable. Interestingly, our research has revealed a correlation between ionic conductivity and mechanical properties in both the SPE and si-SPE series. Ionic conductivity increases as glass transition temperature, α relaxation temperature, and storage modulus decrease, suggesting that Li+ transport is influenced by polymer chain flexibility and Li+/EO interaction.

Influence of Carbon Black on Conductivity and Structure of Polyethylene Oxide Based Polymer Electrolyte Film

AbstractThe potential applications of carbon black are expected to grow as science and technology improve offering up new possibilities for innovation throughout disciplines included in the field of energy storage. The present work shows the influence of carbon black to improve the ionic conductivity of the polymer electrolyte. The synthesis of polyethylene oxide: ammonium iodide based polymer electrolyte incorporated with carbon black varying from 0.01 to 0.06 wt% with respect to PEO: NH4I system by solution casting method. Different characterizations like polarized optical microscopy (POM), impedance spectroscopy, and ionic transference number (tion) are studied in detail. The maximum ionic conductivity is achieved at 0.05 wt% carbon black shows 1.20 × 10−5 S cm−1 at ambient temperature. In accordance with POM data, the amorphous region has increased whereas the crystalline region has shrunk which further indicated the increase in ionic conductivity. The value of (tion) is calculated to be 0.97 which shows the system is ionic in nature. PEO based polymer electrolyte doped carbon black can be used for the fabrication of energy storage devices.

Unconventional PEO-PPC quasi-solid state blend polymer electrolyte for high efficiency solid-state Li-metal batteries

Polymer electrolytes represent a safer alternative over traditional liquid electrolytes, enabling the use of higher energy density active materials as electrodes for batteries. Among the wide variety of different polymeric matrix that are currently been proposed, polyethylene oxide (PEO) is considered one of the most promising. In this work, a PEO-based quasi-solid polymer electrolyte (QSPE) was produced by easily scalable solution casting technique, optimized with addition of plasticizers and blended with polypropylene carbonate (PPC). The resulting polymer electrolyte was ultimately supported to glass fiber separator. Improvement of ionic conductivity, transfer number and electrochemical stability window of the different formulations was confirmed through electrochemical impedance spectroscopy and linear sweep voltammetry. Plating and stripping tests in symmetric LiLi cells and charge–discharge tests in half-cell configuration (Li vs LFP) were performed to evaluate the cyclability and stability of the QSPEs. The PEO-PPC polymer electrolyte showed improved efficiency and stability during charge–discharge cycles, at room temperature, suggesting the positive effect of the presence of carbonate groups in the polymer matrix. The promising results demonstrate that the as-prepared QSPE could represent a feasible and viable alternative to conventional liquid electrolytes and could accelerate the adoption of high energy density storage systems, like Li-metal batteries.

Different-grain-sized boehmite nanoparticles for stable all-solid-state lithium metal batteries.

PEO is one of the common composite polymer electrolyte vehicles; however, the presence of crystalline phase at room temperature, high interface impedance, and low oxidation resistance (<4.0 V) limit its application in stable all-solid-state lithium metal batteries. Herein, we designed a PEO-based solid polymer electrolyte (SPE) by adding boehmite nanoparticles to address the above-mentioned issues. Different-grain-sized boehmite nanoparticles were synthesized by adjusting the hydrothermal temperature. Moreover, the impacts of these distinct grain-sized boehmite nanoparticles used to fabricate boehmite/PEO polymer electrolytes (BPEs) on the performance of all-solid-state lithium metal batteries were investigated. It was found that with the increase in boehmite's grain size, BPEs show better performance. The best BPE exhibited an improved Li+ transference number (0.59), high ionic conductivity (1.25 × 10-4 S m-1), and wide electrochemical window (∼4.5 V) at 60 °C. The assembled lithium symmetric battery can stably undergo 500 hours of lithium plating/stripping at 0.1 mA cm-2. At the same time, the LiFePO4/BPE/Li battery exhibits excellent cycling stability after 100 cycles at 0.5C. This reasonable design strategy with a superior capacity retention rate (86%) demonstrates great potential in achieving high ionic conductivity and good interface stability for all-solid-state lithium metal batteries simultaneously.

Janus nanofibers with multiple Li+ transport channels and outstanding thermal stability for all-solid-state composite polymer electrolytes

Herein, PEO-based composite polymer electrolytes enhanced by Janus nanofibers with multiple Li+ transport channels and outstanding thermal stability were prepared, which exhibit ultra-long cycle stability in all-solid-state lithium metal batteries.

The deconstruction of a polymeric solvation cage: a critical promotion strategy for PEO-based all-solid polymer electrolytes

PEO could be regarded as a macromolecular version of G4, Li+-transport is hindered by its multi-scale polymer structure. A strategy loosening the chain entanglement and tight (EO)n–Li+ interaction is established to improve the Li+-transport of PEO.

Pentafluorobenzene boronic acid with strong Lewis acidity for the modification of PEO-based polymer electrolytes

PFBBA modifies PEO-based electrolytes by endowing B atoms with stronger Lewis acidity and forming a LiF/Li–B–O rich SEI film.

Investigation on the mechanical integrity of a PEO-based polymer electrolyte in all-solid-state lithium batteries.

Polyethylene oxide (PEO)-based solid polymer electrolytes (SPEs) have good ionic conductivity and flexibility, and is a key component of all-solid-state lithium batteries (ASSLBs). Therefore, the mechanical integrity of PEO-based SPEs during cell operation needs to be urgently evaluated. Here, we conducted a series of tensile and shear adhesion performance tests on PEO16-LiTFSI electrolyte and LiFePO4 electrode adhesion samples at various temperatures and quenching rates. Based on the interface performance data and the elastic-viscoplastic material model of the PEO-LiTFSI electrolyte, a comprehensive electrochemical-mechanical model was established to analyze the stress in the cell and evaluate the mechanical integrity of the PEO16-LiTFSI electrolyte and SPE/cathode interface. The experimental results show that the adhesion strength of the SPE and cathode decreases significantly with increasing operating temperature and quenching rate. The simulation study indicates that the mechanical properties of the SPE can be fully utilized to a certain extent by increasing the quenching rate. In addition, appropriately increasing the operating temperature helps maintain the mechanical integrity of the SPE during cell operation. However, increasing the quenching rate and operating temperature will reduce the interface bonding properties between the SPE and the cathode, resulting in an increased probability of mechanical failure at the SPE/cathode interface. To suppress this negative effect, a design scheme to maintain the structural integrity of the PEO-based polymer electrolyte is proposed by using the C-rate and the SPE thickness as control parameters, which can assist in engineering design and safe operation of Li/PEO16-LiTFSI/LiFePO4 for ASSLBs.

Functional Sulfate Additive-Derived Interfacial Layer for Enhanced Electrochemical Stability of PEO-Based Polymer Electrolytes.

Solid-state electrolyte batteries have attracted significant interest as promising next-generation batteries due to their achievable high energy densities and nonflammability. In particular, curable polymer network gel electrolytes exhibit superior ion conductivity and interfacial adhesion with electrodes compared to oxide or sulfide solid electrolytes, bringing them closer to commercialization. However, the limited electrochemical stability of matrix polymers, particularly those based on poly (ethylene oxide) (PEO), presents challenges in achieving stable electrochemical performance in high-voltage lithium metal batteries. Here, these studies report a sulfate additive-incorporated thermally crosslinked gel-type polymer electrolyte (SA-TGPE) composed of a PEO-based polymer matrix and a functional sulfate additive, 1,3-propanediolcyclic sulfate (PCS), which forms stable interfacial layers on electrodes. The electrode-electrolyte interface modified by the PCS enhances the electrochemical stability of the polymer electrolyte, effectively alleviating decomposition of the PEO-based polymer matrix on the cathode. Moreover, it also mitigates side reactions of the Ni-rich NCM cathode and dendrites of lithium metal anode. These studies provide a novel perspective by utilizing interfacial modification through electrolyte additives to resolve the electrochemical instability of PEO-based polymer electrolytes in high-voltage lithium metal batteries.

Towards All-Extruded Custom-Shape Batteries

The rapid growth of flexible electronics for wearable devices, on-skin or environmental sensors, and flexible displays have resulted in intensive research in the field of free form-factor energy-storage systems. Since batteries must withstand bending, folding, or stretching while maintaining their electrochemical performance, the design and processing of battery components, must be reconsidered. Moreover, there is a clear tendency to shift battery technology to clean and cost-effective dry methods with no toxic solvents. Dry fabrication methods are environmentally friendly, involve lower energy consumption, shorter time and are cost-effective. Hot-pressing and melting-extrusion strategies are appropriate for the fabrication of flexible, solid-polymer electrolytes and electrodes with high contents of active materials and high mass loading.Here we present the progress towards the simple, one-step extrusion of a solid-state battery with a multi-shell and layered architecture. Such structures fundamentally minimize the ionic pathway for Li+. As in the conventional battery, high ionic conductivity of extruded electrolyte and compatibility with electrode materials, are the essential properties for enabling high performance of the battery. The electrolytes are composed of LiTFSI, polyethylene oxide (PEO), which is a known lithium-ion conductor, and thermoplastic recyclable and biodegradable polymer- polyurethane (TPU) - for enhanced mechanical properties and high-temperature durability. The extruded electrolytes of different PEO-to-TPU ratios and salt content were characterized by means of ESEM imaging, mass spectroscopy, differential-scanning calorimetry (DSC), electrochemical-impedance spectroscopy (EIS) and solid-state nuclear magnetic resonance (NMR) diffusion measurements. The structure and electrochemical properties of extruded electrolytes were compared with cast films. It was found that TPU, having in its structure, both soft segments from polyol regions and hard segments from isocyanate not only improves the mechanical properties of neat PEO-based polymer electrolyte, but also forms complexes with lithium salt and serves as a conducting medium. Bulk conductivity vs. temperature dependencies obey Arrhenius behavior. The highest conductivity values varying from 0.3 to 1mS/cm over a temperature range from RT to 90ºC were achieved for the extruded 1:15 (Li:EO) solid polymer electrolyte. The NMR tests show that lithium self-diffusion coefficients in extruded PE with alumina filler are close to that in cast PE, but the anion diffusion coefficients (accessible through 19F NMR) are lower in extruded filaments, indicating a correspondingly higher Li+ transference number induced by the extrusion. Lithium cells with extruded LFP cathode and solid extruded polymer electrolyte demonstrated 40 reversible cycles with close to 96% coulombic efficiency. The electrochemical performance of half-cells composed of extruded LFP-based cathode and extruded TPU-MWCNT-based current collector will be presented.

Multifunctional single-ion conductor-integrated PEO-based solid polymer electrolytes endow highly stable and dendrite-free lithium metal batteries

Poly(ethylene oxide) (PEO) based solid polymer electrolytes (SPEs) hold great promise for circumventing the safety issues caused by liquid electrolytes, which are widely used as one of the leading technical strategies for constructing solid-state lithium metal batteries (LMBs). Unfortunately, developing PEO-based SPEs applicable to high-performance LMBs remains challenging due to the uncontrolled formation of lithium dendrites and sluggish ion migration. In this study, we present the fabrication of highly conductive and mechanically robust composite SPEs (CSPEs) for use in dendrite-proof LMBs by adding a new bis(sulphonyl)imide-based single-ion conductor (LiPEBI) as functional polymer fillers into PEO SPEs network. As expected, the as-prepared CSPEs can simultaneously achieve an excellent mechanical strength of 2.1 MPa, a considerable elongation at a break of 1491.0%, and an optimized degree of crystallization of 37.1%. In addition, introducing the LiPEBI additive promotes the homogeneous distribution of Li-ions and accelerates the ionic transport, resulting in an enhanced ionic conductivity of 4.17 × 10−4 S cm−1 and lithium ion transference number (tLi+) of 0.45 at 60 °C for CSPEs. Such comprehensive physical and electrochemical performances are favorable to suppressing lithium dendrite growth and prolonging the lifespan of LMBs. As a result, the Li||Li symmetrical cells assembled by the CSPEs display a remarkably stable cyclic performance with an extremely low voltage polarization of 60.3 mV over 500 h under 50 μA cm−2 at 60 °C. Also, the CSPEs-based Li||LiFePO4 batteries illustrate superior rate performance up to 1 C and deliver long-term cycling stability with a high discharge capacity of 128.8 mAh g−1 after 100 cycles under 0.4 C at 60 °C. We believe the novel CSPEs have great potential for actual application in the construction of high-safety and dendrite-free solid-state LMBs.

Effect of directional arrangement one-dimensional Fe3O4-coated sepiolite structure on the Li+ conduction of PEO-based polymer electrolyte

The low Li+ conductivity and high cost of polyethylene oxide (PEO)-based polymer electrolytes still restrict their application. Herein, a natural one-dimensional sepiolite (SEP) material is coated with Fe3O4 (FSEP) to construct a FSEP-PEO composite polymer electrolyte (CPE) with a directional arrangement structure, which significantly improved the Li+ conductivity. Results show that the Li+ conductivity of CPE (9.1 ×10−5 S cm−1) based on vertical arrangement FSEP is 43 times higher than that of PEO (2.1 ×10−6 S cm−1), and 9.1 times and 3.1 times higher than that of parallel (1.0 ×10−5 S cm−1) and disordered arrangement (2.9 ×10−5 S cm−1), respectively. The arrangement direction of FSEP has no obvious effect on the crystallinity of PEO and the dissociation degree of LiTFSI, while it has a great influence on the Li+ migration number (tLi+). The tLi+ of CPE with vertical arrangement (0.333) increased by 99.4% compared with that of the parallel arrangement (0.167), suggesting a short and fast migration path. Through multi-physical field simulation, the high current density in CPE is mainly distributed at the FSEP/PEO interface, indicating that the FSEP/PEO interface plays a dominant role in Li+ conduction. In addition, lithium symmetric batteries and LiFePO4 batteries based on vertically arranged CPE have excellent cycle and rate performance.

Effect of anion size and salt concentration on ion transport in PEO-based solid polymer electrolytes at high temperatures

Effect of anion size and salt concentration on ion transport in PEO-based solid polymer electrolytes at high temperatures

A flexible PEO-based polymer electrolyte with cross-linked network for high-voltage all solid-state lithium-ion battery

Solid state lithium-ion batteries (SLIBs) have been considered as one of the most promising sustainable next-generation technologies for energy storage. However, the poor interfacial compatibility and low ion conductivity of solid electrolytes still remain a major challenge for SLIBs. Herein, a free-standing flexible solid polymer LA-PAM-PEO electrolyte is constructed through the electrospinning technology featuring with high Li+ conductivity (6.1 × 10−4 S cm−1), strong mechanical strength and high Li+ migration number (0.32), which breaks the restriction between ionic conductivity and mechanical strength in polymer solid electrolyte. The cross-linking between LA, PAM and PEO is verified to decrease the crystalline of PEO, thus increasing the Li+ conductivity. Moreover, benefiting from the 3D network composed of interconnected nanofibers and the covalent bonds between LA, PAM and PEO, the mechanical strength of LA-PAM-PEO SPE was also effectively improved. The LA-PAM-PEO SPE also delivers a high electrochemical window (4.95 V), and low interface resistance (243.8 Ω). As a result, the Li/Li symmetrical cell with the LA-PAM-PEO displayed outstanding stability after 1000 h with the uniform Li deposition on the interface of Li electrode, in sharp contrast to the PEO SPE. In addition, the Li/LA-PAM-PEO SPE/LFP displays a discharge capacity of 135 mA h g−1 after 1000 cycles at the rate of 1 C, with a capacity retention of 93.5%. The proposed LA-PAM-PEO SPE thus opens new possibilities for the fabrication and engineering of solid-state Li-ion batteries.

PEO-Based Solid Composite Polymer Electrolyte for High Capacity Retention All-Solid-State Lithium Metal Battery.

The limited ionic conductivity at room temperature and the constrained electrochemical window of poly(ethylene oxide) (PEO) pose significant obstacles that hinder its broader utilization in high-energy-density lithium metal batteries. The garnet-type material Li6.4 La3 Zr1.4 Ta0.6 O12 (LLZTO) is recognized as a highly promising active filler for enhancing the performance of PEO-based solid polymer electrolytes (SPEs). However, its performance is still limited by its high interfacial resistance. In this study, a novel hybrid filler-designed SPE is employed to achieve excellent electrochemical performance for both the lithium metal anode and the LiFePO4 cathode. The solid composite membrane containing hybrid fillers achieves a maximum ionic conductivity of 1.9 × 10-4 S cm-1 and a Li+ transference number of 0.67 at 40°C, respectively. Additionally, the Li/Li symmetric cells demonstrate a smooth and stable process for 2000 h at a current density of 0.1mA cm-2 . Furthermore, the LiFePO4 /Li battery delivers a high-rate capacity of 159.2 mAh g-1 at 1 C, along with a capacity retention of 95.2% after 400 cycles. These results validate that employing a composite of both active and inactive fillers is an effective strategy for achieving superior performance in all-solid-state lithium metal batteries (ASSLMBs).

Semi-interpenetrating-network PEO-based polymer electrolytes with fast Li-ion conduction for solid Li-metal batteries

Semi-interpenetrating-network (semi-IPN) PEO-based solid polymer electrolytes (SPEs) are synthesized for the application of Li-metal batteries. Owing to the special semi-IPN structure and synergistic effects of EO segments and PVDF-HFP, the SIN solid electrolytes demonstrate great flexibility, high ionic conductivity of 2.45 × 10−4 S cm−1 at 25 °C, outstanding thermal stability and broad electrochemical window (4.9 V vs. Li+/Li). In addition, SIN owns excellent electrochemical stability with Li-metal with a low over-potential <70 mV after 1400 h Li plating/stripping. Moreover, benefiting from the stable interfacial contact, LiFePO4|SIN|Li cells provide high discharge capacity of 146 mAh g−1 with superior capacity retention of 96.6 % after 500 cycles at 0.1C under room temperature. Hence, the semi-IPN PEO-based SPEs appear to be promising for use in high-performance solid-state Li-metal batteries.