Recent progress of composite solid polymer electrolytes for all-solid-state lithium metal batteries

In comparison with lithium-ion batteries (LIBs) with liquid electrolytes, all-solid-state lithium batteries (ASSLBs) have been considered as promising systems for future energy storage due to their safety and high energy density. As the pivotal component used in ASSLBs, composite solid polymer electrolytes (CSPEs), derived from the incorporation of inorganic fillers into solid polymer electrolytes (SPEs), exhibit higher ionic conductivity, better mechanical strength, and superior thermal/electrochemical stability compared to the single-component SPEs, which can significantly promote the electrochemical performance of ASSLBs. Herein, the recent advances of CSPEs applied in ASSLBs are presented. The effects of the category, morphology and concentration of inorganic fillers on the ionic conductivity, mechanical strength, electrochemical window, interfacial stability and possible Li⁺ transfer mechanism of CSPEs will be systematically discussed. Finally, the challenges and perspectives are proposed for the future development of high-performance CSPEs and ASSLBs.     

Polyacrylonitrile-based gel polymer electrolyte filled with Prussian blue forhigh-performance lithium polymer batteries

Lithium polymer batteries(LPBs) rely on a high ion transport to gain improved cell performance.Thermostable and porous gel polymer electrolytes(GPEs) have attracted much attention due to their excellent properties in electrolyte wettability and ionic conductivity.In this work,iron-nickel-cobalt trimetal Prussian blue analogue(PBA) nanocubes are filled into the electro spun polyacrylonitrile(PAN)-based membranes to generate GPE composites with morphological superiority consisting of fine fibers and interconnected pores.The thus obtained PBA@PAN fibrous membrane showcases good thermal stability,high porosity and electrolyte uptake,as well as a peak io nic conductivity of 2.7 mS/cm with the addition of 10% PBA,Consequently,the assembled lithium iron phosphate(LiFePO_4) battery using PBA@PAN-10 as the GPE delivers a high capacity of 152.2 mAh/g at 0.2 C and an ultralow capacity decay of0.09% per cycle in a long-te rm cycle life of 350 cycles at 1 C,endorsing its promising applications in LPBs.     

Study of the interaction polymer/organic solvents/salt in microporous PVdF separator for lithium batteries

Interactions between microporous PVdF and polar liquid electrolytes have been investigated. PVdF separators are an attractive alternative to microporous apolar polyolefins, such as polyethylene, whose poor wetting by these electrolytes induces a significant resistivity increase in lithium batteries. The swelling study of polymer/electrolyte interactions has shown that the resistivity increase induced by microporous PVdF is moderate and will enable the electrolyte composition to be optimized. Existence of a shut-down effect is an asset for the battery safety.     

Review on gel polymer electrolytes for lithium batteries

This paper reviews the state-of-art of polymer electrolytes in view of their electrochemical and physical properties for the applications in lithium batteries. This review mainly encompasses on five polymer hosts namely poly(ethylene oxide) (PEO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF) and poly(vinylidene fluoride-hexafluoro propylene) (PVdF-HFP) as electrolytes. Also the ionic conductivity, morphology, porosity and cycling behavior of PVdF-HFP membranes prepared by phase inversion technique with different non-solvents have been presented. The cycling behavior of LiMn₂O₄/polymer electrolyte (PE)/Li cells is also described.     

The network gel polymer electrolyte based on poly(acrylate-co-imide) and its transport properties in lithium ion batteries

Poly (acrylate-co-imide)-based gel polymer electrolytes are synthesized by in situ free radical polymerization. Infrared spectroscopy confirms the complete polymerization of gel polymer electrolytes. The ionic conductivity of gel polymer electrolytes are measured as a function of different repeating EO units of polyacrylates. An optimal ionic conductivity of the poly (PEGMEMA₁₁₀₀-BMI) gel polymer electrolyte is determined to be 4.8 × 10^–3 S/cm at 25 °C. The lithium transference number is found to be 0.29. The cyclic voltammogram shows that the wide electrochemical stability window of the gel polymer electrolyte varies from −0.5 to 4.20 V (vs. Li/Li⁺). Furthermore, we found the transport properties of novel gel polymer electrolytes are dependent on the EO design and are also related to the rate capability and the cycling ability of lithium polymer batteries. The relationship between polymer electrolyte design, lithium transport properties and battery performance are investigated in this research.     

All solid polymer electrolytes based on polar side group rotation for rechargeable lithium batteries

A novel polymer matrix with a polar carbonyl group was designed and used to prepare an all‐solid polymer electrolyte in lithium rechargeable batteries. The ionic conductivity of this type of polymer electrolyte was examined. The relationship between the lithium salt concentration and ionic conductivity was investigated by Fourier transform infrared (FTIR) spectroscopy. The carbonyl groups in the polymer matrix effectively interacted with the lithium salt, which improved the ionic conductivity at a large range of temperatures. The ionic conductivity of this type of polymer electrolyte was approximately 10^?4 S cm^?1 at room temperature. The stability of the interface between electrode and electrolyte was evaluated by measuring the alternating current (AC) impedance. Copyright © 2009 John Wiley & Sons, Ltd.     

Designing composite polymer electrolytes for all-solid-state lithium batteries

Ceramic fast-ion conductors have high ionic conductivities (>10^?4 S cm^?1) but are difficult to process and have poor chemo/mechanical properties at the electrode/electrolyte interfaces. In contrast, polymer electrolytes are pliable and easy to process but suffer from low room-temperature ionic conductivities (≈10^?6-10^?7 S cm^?1). Combining these two elements to form a composite polymer electrolyte is a promising way to enable all-solid-state lithium-metal batteries. The choice of ceramic filler and polymer can be tailored to provide synergistic benefits that overcome the practical shortcomings of the two components. Herein, the fundamentals of Li⁺ conduction through the various phases and interfaces in these materials are discussed as well as the important parameters, beyond the initial choice of polymer and ceramic filler materials that must be considered while designing composite polymer electrolytes. Emphasis is placed on the particle filler engineering and practical fabrication methods as routes toward enhancing the properties of these composites.     

Synthesis and electrochemistry of polymer based electrolytes for lithium batteries

An overview is presented on the development of improved polymer based electrolytes during the past years. The emphasis lies on new approaches regarding chemical concepts that achieve a higher total conductivity and lithium transference number as well as an increased electrochemical, mechanical and thermal stability. With respect to the polymer chemistry, the focus is laid on siloxane and phosphazene derived systems. Topics are the chemical modification of the polymeric, cyclic and low molecular derivates of these systems, the formation of stable membranes from these by suitable cross-linking strategies and an extensive electrochemical characterization in corresponding lithium cells. Recent trends towards composite and hybrid materials are illustrated with examples and newly developed hybrid electrolytes. A particular chance for improvements comes from the design and use of stable small molecular additives in combination with optimized and electrochemically stable polymer networks. Special compounds are introduced which may act themselves as novel solvents with increased electrochemical stabilities. The relevance of chosen lithium salts for polymer electrolytes is discussed, too, and a new family of pyrazolide anions is introduced. In all cases, the electrochemical performance has been characterized by standard experimental techniques.     

Nonflammable nonaqueous electrolytes for lithium batteries

As the energy density of state-of-the-art lithium (Li)-ion batteries (LIBs) increases, the safety concern of LIBs using liquid electrolytes is drawing increasing attention. Flammability of electrolytes is a critical link of the overall safety performance of LIBs and Li metal batteries. For this reason, intensive efforts have been devoted to suppressing the flammability of liquid electrolytes. In this short review, the common approaches to reduce the flammability of the nonaqueous liquid electrolytes will be summarized. The advantages and limitations of these approaches will also be discussed.     

Highly porous LiMnPO4 in combination with an ionic liquid-based polymer gel electrolyte for lithium batteries

A porous well defined LiMnPO₄ cathode material is synthesized by a sol-gel method. The electrochemical performance of the cathode material is evaluated in a cell with an ionic liquid-based polymer electrolyte (0.5 M LITFSI in EMImTFSI) and a lithium metal electrode. The results are compared to a cell with a traditional organic carbonate-based electrolyte (1 M LiPF₆ in EC/DMC). The cell with the ionic liquid-based polymer electrolyte presents an enhanced electrochemical intercalation performance of lithium ions, a high electrochemical stability window of 5 V, and an excellent cycling ability as compared with the organic based counterpart. Furthermore, the ionic liquid-based polymer gel electrolyte effectively prevents the dissolution of manganese — otherwise a common problem.     

Internal in situ gel polymer electrolytes for high-performance quasi-solid-state lithium ion batteries

Journal of Solid State Electrochemistry - The performance of solid-state lithium ion battery mainly depends on the performance of the electrolyte and the interface between the electrolyte and the...     

Recent progress in liquid electrolytes for lithium metal batteries

Li metal batteries are revived as the next-generation batteries beyond Li-ion batteries. The Li metal anode can be paired with intercalation-type cathodes LiMO₂ and conversion-type cathodes such as sulfur and oxygen. Then, energy densities of Li/LiMO₂ and Li/S,O₂ batteries can reach 400 Whkg^?1 and more than 500 Whkg^?1, respectively, which surpass that of the state-of-the-art LIB (280 Whkg^?1). However, replacing the intercalation-type graphite anode with the Li metal anode suffers from low coulombic efficiency during repeated Li plating/stripping processes, which leads to short cycle lifetime and potential safety problems. The key solution is to construct a stable and uniform solid electrolyte interphase with high Li⁺ transport and high elastic strength on the Li metal anode. This review summarizes recent progress in improving the solid electrolyte interphase by tailoring liquid electrolytes, a classical but the most convenient and cost-effective strategy.     

Novel siloxane polymers as polymer electrolytes for high energy density lithium batteries

A variety of disubstituted (double-comb) polysiloxane polymers have been prepared containing linear, branched, and cyclic oligoethyleneoxide units, –(OCH₂CH₂)_n–, in the side chains and as part of the siloxane backbone. Copolymers, using mixtures of linear ethylene oxide side chains, were also synthesized. These polymers were doped with LiN(SO₂CF₃)₂ (LiTFSI, 1) and conductivities of the polymer-salt complexes were determined as a function of temperature and doping level. The maximum conductivity of these polymers at 25 ° C was 2.99 ×10^–4, for a copolymer containing equimolar amounts of side chains with n = 5 and 6.     

固态聚合物电解质的锂离子传导机理与研究进展

锂离子电池(lithiumionbatteries,LIBs)在储能领域已取得了巨大的成功.然而,商用LIBs含有高挥发性易燃有机电解液,使其存在严重的安全隐患.固态聚合物电解质具有解决相应安全性问题的潜力,有望成为下一代高安全性全固态LIBs的电解质材料.然而,固态聚合物电解质存在离子电导率不高等问题,限制了其在固态LIBs中的实际应用.研究者们为了提高该类电解质的离子电导率、锂离子迁移数等综合电化学性能,已在寻找新锂盐、对聚合物进行改性以及向聚合物电解质中添加填料等方面进行了较多的研究.本文简要概述了固态聚合物电解质的锂离子传导机理以及在提高固态聚合物电解质综合电化学性能方面的研究进展.     

A novel gel polymer electrolyte based on poly ionic liquid 1-ethyl 3-(2-methacryloyloxy ethyl) imidazolium iodide

Poly ionic liquid 1-ethyl 3-(2-methacryloyloxy ethyl) imidazolium iodide (PEMEImI) as a single-ion conductor was designed and synthesized. When appropriate amount of suitable plasticizers, I₂ and polyacrylonitrile (PAN) were incorporated into it, the complex formed gel polymer electrolyte. Chemical structure, thermal behavior and ionic conductive properties of the gel polymer electrolyte were investigated by Raman spectra, UV-Vis spectra, differential scanning calorimetry (DSC), and complex impedance analysis, respectively. For the new gel polymer electrolyte, the ionic conductivity of about 1 × 10⁻³ S cm⁻¹ at room temperature was achieved.     

Poly(vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) based composite electrolytes for lithium batteries

The composite polymer electrolyte (CPE) membranes, comprising of poly(vinylidene fluoride-hexafluoropropylene) (PVdF-HFP), aluminum oxyhydroxide, (AlO[OH]_n) of two different particle sizes 7 μm/14 nm and LiN(CF₃SO₂)₂ as lithium salt were prepared using solution casting technique. The prepared membranes were subjected to XRD, impedance spectroscopy, compatibility and transport number studies. The incorporation of nanofiller greatly enhanced the ionic conductivity and the compatibility of the composite polymer electrolyte. Also LiCr_0.01Mn_1.99O₄/CPE/Li cells were assembled and their charge-discharge profiles have been made at 70 °C. The film which possesses nanosized filler offered better electrochemical properties than those with micron sized filler. The results are discussed based on Lewis acid-base theory.     

Study of the role of ceramic filler in composite gel electrolytes based on microporous polymer membranes

The presented contribution aims at reconsidering the role of filler in affecting the ionic transport in composite gel electrolytes for Li-ion cells based on microporous polymer membranes. The gels have been prepared by swelling thin PVdF/HFP membranes either with conventional liquid electrolyte or with pure propylene carbonate solvent. The membranes contained dispersed submicron-size modified silica filler added in a wide range of weight ratios. The effect of filler content on the kinetics of liquid phase absorption and evaporation from the composite membranes, as well as on the conductivity of the corresponding gel electrolytes, has been studied and discussed in terms of the “colloidal” and “soggy sand” electrolyte concepts. It has been found that conductivity increase of composite gels is not directly correlated with the liquid electrolyte uptake. On this basis it is concluded that important part of ionic transport in this type of composite gel polymer electrolytes is realized on the filler grain boundaries, through overlapping space charge layers of the silica grains.     

Composite gel membranes: a new class of improved polymer electrolytes for lithium batteries

Novel composite, gel-type polymer electrolytes have been prepared by dispersing selected ceramic powders into a matrix formed by a lithium salt solution contained in a poly(acrylonitrile) (PAN) network. The electrochemical characterization demonstrates that these new types of composite gel electrolytes have high ionic conductivity, wide electrochemical stability and, particularly, high chemical integrity (no liquid leakage) even at temperatures above ambient. These unique properties make the composite gel membranes particularly suitable as electrolyte separators in lithium ion polymer batteries.     

Preparation and performance characterization of polymer Li-ion batteries using gel poly(diacrylate) electrolyte prepared by in situ thermal polymerization

A gel polymer electrolyte (GPE) was prepared by in-situ thermal polymerization of 1,3-butanediol diacrylate (BDDA) in a EC/EMC/DMC electrolyte solution at 100 °C. The GPE with 15 wt.% polymer content appears as apparently dry polymer with sufficient mechanical strength and shows a high ionic conductivity of 3.2×10^–3 S cm^–1 at 20 °C. The MCMB–LiCoO₂ type polymer Li-ion batteries (PLIB) prepared using this in-situ internal polymerization method exhibit a very high initial charge–discharge efficiency of 92.1%, and can deliver 94.4% of its nominal capacity at 1.0 C rate and 70.7% of its room temperature capacity at –20 °C. Also, the PLIB cells show very good cycling ability with >85% capacity retention after 300 cycles. The excellent charge–discharge properties of the PLIB cells are attributed to the integrated structure in which the polymer matrix spreads over entire region of the cell acting as a strong binder and electrolyte carrier to produce a stabilized electrode–electrolyte interface. In addition, the fabricating process of the polymer cell is quite simple and convenient for practical applications.     

Block copolymer electrolytes for rechargeable lithium batteries

Ion‐conducting block copolymers (BCPs) have attracted significant interest as conducting materials in solid‐state lithium batteries. BCP self‐assembly offers promise for designing ordered materials with nanoscale domains. Such nanostructures provide a facile method for introducing sufficient mechanical stability into polymer electrolyte membranes, while maintaining the ionic conductivity at levels similar to corresponding solvent‐free homopolymer electrolytes. This ability to simultaneously control conductivity and mechanical integrity provides opportunities for the fabrication of sturdy, yet easily processable, solid‐state lithium batteries. In this review, we first introduce several fundamental studies of ion conduction in homopolymers for the understanding of ion transport in the conducting domain of BCP systems. Then, we summarize recent experimental studies of BCP electrolytes with respect to the effects of salt‐doping and morphology on ionic conductivity. Finally, we present some remaining challenges for BCP electrolytes and highlight several important areas for future research. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1–16