Твердые полимерные электролиты на основе полиуретанового эластомера для твердотельных суперконденсаторов

<p indent="0mm">Since the commercialization of lithium-ion batteries in the 1990s, lithium-ion batteries have been successfully applied in portable electronics, electric vehicles, and grid energy storage. Although current organic liquid electrolytes have high ionic conductivities, they are inherently flammable, volatile, and prone to leakage. Moreover, severe side reactions and dendrite growth on the surface of the lithium anode during the charge-discharge process can cause safety hazards, which greatly impede their applications in lithium metal batteries. Solid electrolytes, including inorganic solid electrolytes and polymer electrolytes, are regarded as effective alternatives to organic liquid electrolytes for the construction of lithium metal batteries with high energy density and safety. Among them, solid polymer electrolytes offer excellent flexibility, processability, and interfacial compatibility over inorganic solid electrolytes, and they are extraordinarily promising for lithium metal batteries with high energy density and safety. Ideal solid polymer electrolytes should have following features: (1) High ionic conductivity (&gt; <sc>10 ^–4 S cm ^–1) </sc> at room temperature; (2) high lithium ion transference number (~1) to reduce the concentration polarization and improve the rate performance of batteries; (3) intimate contact at the electrode/electrolyte interfaces; (4) wide electrochemical window <sc>(&gt;4.5 V</sc> vs. Li/Li ⁺) to match high-voltage cathodes and improve the energy density of batteries; (5) good mechanical stability to resist processing, buffer electrode volume change and inhibit dendrite growth; (6) good thermal stability to withstand environmental changes. Generally, the ionic conductivity of pure solid polymer electrolytes at room temperature is low <sc>(~10 ^–6 S cm ^–1). </sc> Researchers have tried to improve the ionic conductivities by adjusting the lithium salt concentration, such as developing “polymer-in-salt” solid electrolytes. However, increasing the concentration of lithium salt leads to the deterioration of the mechanical strength. Strategies such as developing novel lithium salts, modifying polymer matrix, and incorporating inorganic fillers into solid polymer electrolytes are proposed to promote ionic conductivities of solid polymer electrolytes. In particular, composite polymer electrolytes, fabricated by dispersing a certain amount of inorganic fillers into solid polymer electrolytes, have improved ionic conductivities without sacrificing their mechanical performances. Poor interfacial property between electrodes and electrolytes is also a critical issue for solid polymer electrolytes. On one hand, poor and uneven solid/solid contacts at the electrode/electrolyte interfaces lead to high resistance and sluggish ionic transport kinetics. Furthermore, the volume change of the positive and negative electrodes in the charge/discharge process deteriorates the interfacial contacts, blocks the ion and electron transport through the interfaces, and greatly reduces the electrochemical reaction kinetics. On the other hand, the electrochemical windows of solid polymer electrolytes are usually narrow <sc>(＜4.5 V).</sc> During cycling, redox reactions are prone to occur at the electrode/electrolyte interfaces, causing battery failure. Solid polymer electrolytes have also poor thermal and mechanical stabilities. Therefore, design and synthesis of polymer-based solid electrolytes with excellent comprehensive performances and construction of fast and stable ion transport channels at the electrolyte/electrode interfaces are of great significance for the successful development of solid-state lithium metal batteries. This paper presents a brief review of the research progress in solid polymer electrolytes from two aspects: Improving the ionic conductivities of solid polymer electrolytes and enhancing the interfacial performance at electrolyte/electrode interfaces. First, targeted optimization strategies on ionic conductivities of solid polymer electrolytes, including constructing continuously aligned ionic transport paths and shortening the ionic transport distance, are summarized. Second, interface optimization strategies, including constructing wetting interfaces and synthesizing asymmetric electrolytes, are presented to reduce the interface resistance and improve the interfacial contact. Finally, perspectives on the development of solid polymer electrolytes and high-performance solid-state lithium metal batteries are discussed, and key research directions and advanced test methods are proposed. This review may provide a comprehensive understanding and further guidance for not only the material design of solid polymer electrolytes, but also the structural design of lithium metal batteries with favorable electrochemical and interfacial performances.

Solid polymer electrolytes are considered as key materials in flexible solid‐state supercapacitors. In this work, the polyurethane‐based solid polymer electrolytes were obtained from polyurethane elastomer prepared from toluene diisocyanate (TDI) based prepolymer PFL100 and 3,3′‐dichloro‐4,4′‐diaminodiphenylmethane (MOCA) as polymeric matrix impregnated with lithium tetrafluoroborate LiBF 4 solution in N ‐Methyl‐2‐pyrrolidone (NMP). The swelling degree, mechanical properties and ionic conductivity of the polymer electrolytes were shown to strongly depend on the concentration of LiBF 4 in NMP. The polymer impregnated with the lithium salt solution containing 7 wt.% LiBF 4 (PU‐PFL100) has the optimal mechanical properties, high ionic conductivity (nearly 5 × 10 −4 S cm −1 at 25°C) and was tested as the solid polymer electrolyte for flexible solid‐state supercapacitors with MXene‐activated carbon (MXene/AC) composite electrodes. Symmetrical (MXene/AC//PU‐PFL100//MXene/AC) and asymmetrical (MXene/AC//PU‐PFL100//Li 4 Ti 5 O 12 ) supercapacitor cells were tested in which PU‐PFL100 was used as an electrolyte‐separator. Cyclic voltammetry (CV) and galvanic charge–discharge (GCD) experiments showed that the supercapacitor cells can deliver a specific capacitance about 40 F g −1 at room temperature and PU‐PFL100 can be successfully used in the flexible solid‐state supercapacitors.

Introduction To achieve carbon-neutral society, battery technologies have been attracting attention in recent years owing to its potential for storing renewable energy and serving as a load leveling power sources. In particular, all-solid-state batteries (ASSBs) utilizing non-volatile and flame-resistant solid electrolytes are actively investigated worldwide for practical implementation, as they are expected to enhance safety. Among solid electrolytes, solid polymer electrolytes (SPEs), which exhibit high flexibility and formability, are expected for their application in electrochemical devices such as ASSBs. In SPEs, cations are solvated by the host polymer and occurs ionic conducte through cooperative transport associated with segmental motion. The ionic transport properties of SPE, affected by molecular structures of electrolyte salt, and are further influenced by processes solvation/desolvation of cation and decomposition reactions under electrochemical conditions, is considered different from static states. Therefore, we focused on applying [Li | SPE | Li] symmetric cells and evaluated the ionic transport processes within SPE under reaction conditions using concentration changes through operando Raman spectroscopy measurements. In this study, we applied the measurement approach for use on SPEs incorporating LiN(SO2F)2 (LiFSA), LiN(SO2CF3)2 (LiTFSA), and LiN(SO2C2F5)2 (LiBETI) as Li salts to investigate the impact of anion structure/molecular weight on ionic transport mechanisms under actual reaction conditions. Experiments Li-based solid polymer electrolytes were prepared by mixing cross-linked polyether-based macromonomer P(EO/PO) (EO: PO = 8:2), Li salts (LiFSA, LiTFSA, LiBETI), and photopolymerization initiator DMPA in acetonitrile under an Ar atmosphere within a glovebox. The resulting solution was vacuum-dried and filled between glass plates using a spacer (thickness: 0.5 mm). Each SPE film was then fabricated by UV irradiation. To investigate the solvation structure and salt dissociation characteristics of SPE (salt concentration: [Li]/[O] = 0.04-0.16) under static conditions, Raman spectroscopy measurements were performed (NRS-4500: Jasco). A 9 mm × 9 mm rectangular-shaped [Li | SPE([Li]/[O]=0.04, 0.16) | Li] symmetric cell was prepared for in situ monitoring of concentration variations into the SPE during electrochemical reactions. The symmetric cell was introduced into a sealed cell with a quartz glass having monitoring window and connected to a potentiostat (HZ-7000, Hokuto Denko). In o perando Raman spectroscopy, Raman spectra were obtained from the vicinity of the working electrode (W.E.) and the counter electrode (C.E.) within the SPE during voltage application. The W.E. and C.E. regions were measured at points approximately 10-30 µm from the electrode/electrolyte interface. Results & Discussion Raman spectrum of the P(EO/PO)-LiTFSA(1) and LiBETI(2) system exhibited the peak at approximately 740 cm-1 derived from SNS vibration of TFSA and BETI anion. This peak, which increases with salt concentration, can be utilized as an indicator to evaluate concentration changes within the SPE induced by electrode reactions. To evaluate the ionic transport properties, operand o Raman spectroscopy measurements were performed using [Li | SPE([Li]/[O]=0.04, 0.16)|Li] symmetry cells. The peak area change (A/A 0) from the initial state was calculated by using the obtained Raman spectra. Fig. 1 and 2 exhibited the relationship between A/A 0 and applied voltage time calculated from measured points near W.E. and C.E. in symmetrical cells using the LiTFSA and LiBETI systems. In both Fig. 1 and 2, the peak area changes (A/A 0) were observed that concentrations near W.E. and C.E. increased or decreased with voltage application. In particular, the peak area changes (A/A 0) of the LiTFSA system exhibited a rapid increase in W.E. and decrease in C.E. within the initial 1 h of measurement, followed by no significant changes over 5 h (Fig. 1). This result suggests that the SPE has reached a steady state within at the end of the experiment. And in Fig. 1, the area changes (A/A 0) of [Li]/[O]=0.04 was significantly higher than that of [Li]/[O]=0.16. This results suggests that the faster ionic transport characteristics of [Li]/[O]=0.04 compared to [Li]/[O]=0.16 can be attributed to the lower concentration of the former. No significant changes were observed both [Li]/[O]=0.04 and 0.16 owing to changes in A/A 0, similar to LiTFSA system (Fig. 2). The lower ionic transport properties of LiBETI can be attributed to the larger molecular weight of BETI anion. These results indicated that the ionic transport mechanisms under reaction conditions differ depending on the anion structure (molecular weight).(1) I. Rey, et al, J. Electrochem. Soc., 145, 3034 (1998).(2) C. Capiglia, et al., J. Electrochem. Soc., 150, A525 (2003). Figure 1

Rechargeable lithium ion batteries become an very important technology in the contemporary society. They are expanding their application in electric vehicles and power grids. However, current lithium ion batteries with liquid electrolyte have been suffering from potential safety crisis mainly due to their highly flammable organic liquid carbonate organic electrolyte and explosion hazards. These potential risks (combustion and explosion) would retard the commercialization of electric vehicles or hybrid electric vehicles. Thus, the safety issue of lithium ion battery merits further study. Solid electrolytes have attracted ever-increasing interest owing to their enhanced safety issue and higher energy density of lithium battery. Solid electrolyte materials mainly include inorganic solid electrolytes (ISEs) and solid polymer electrolytes (SPEs). The ISEs are classified into oxide-based, sulfide-based and etc. However, in spite of the presence of highly ion conductive ISEs, there are still many undergoing issues that limit the practical application at the present stage, like the large interface impedance between electrode and ISEs and the difficulty of processing. More attention has been paid to solid polymer electrolytes due to their superior flexibility and processability, which are also subjected to thermal expansion at elevated temperature. Poly(ethylene oxide) (PEO) solid polymer electrolyte has undergone a sort of renaissance in the past few decades. However, the quintessential frailty of PEO solid polymer electrolyte is low ionic conductivity (in the order of 10(-7) S cm(-1)) at room temperature with a relatively narrow electrochemical window. Hence, it is essential to develop new solid polymer electrolytes with comprehensive performance in terms of high ionic conductivity, wide electrochemical window, superior mechanical strength, excellent thermal stability as well as good interfacial compatibility. In this review, a series of polycarbonate-based solid polymer electrolytes (such as PEC, PPC, PTMC and PVC et al.) are summarized. In addition, we also present a brief review on preparation, electrochemical property, modification, ionic transportation mechanism and future development direction for each of these solid polymer electrolytes.

Enhancement of electrical and electrochemical properties of sodium bromide incorporated with poly (ethylene oxide)/poly (vinylidene fluoride-hexafluoropropylene) solid blend polymer electrolytes for electrochemical double layer capacitors

Stabilizing Solid Electrolyte-Anode Interface in Li-Metal Batteries by Boron Nitride-Based Nanocomposite Coating

New activated nanoporous carbons, produced by carbonization of mixtures of coal tar pitch and furfural with subsequent steam activation, as well as electrochemically active oxide Li4Ti5O12, prepared by thermal co-decomposition of oxalates, were tested and characterized as electrode materials for electrochemical supercapacitors. The phase composition, microstructure, surface morphology and porous structure of the materials were studied. Pure carbon electrodes as well as composite electrodes based on these materials obtained were fabricated. Two types of supercapacitor (SC) cells were assembled and subjected to charge–discharge cycling study at different current rates: (1) symmetric sandwich-type SC cells with identical activated carbon electrodes and different organic electrolytes, and (2) asymmetric hybrid SC cell composed by activated graphitized carbon as a negative electrode and activated carbon–Li4Ti5O12 oxide composite as a positive electrode, and an organic electrolyte (LiPF6–dimethyl carbonate/ethylene carbonate (DMC/EC). Four types of carbons with different specific surface area (1,000–1,600 m2 g−1) and texture parameters, as well as three types of organic electrolytes: Et4NBF4–propylene carbonate (PC), LiBF4–PC and LiPF6–DMC/EC in the symmetric SC cell, were tested and compared with each other. Capacitance value up to 70 F g−1 for the symmetric SC, depending on the electrolyte microstructure and conductivity of the carbon material used, and capacitance of about 150 F g−1 for the asymmetric SC cell, with good cycleability for both supercapacitor systems, were obtained.

Investigation of hydroxide ion-conduction in solid polymer electrolytes via electrochemical impedance spectroscopy

Despite the low cost and high ionic conductivity of aqueous electrolytes, their practical applications are limited because a low withstand voltage of 1.2 V The energy density increases in proportion to the withstand voltage which is a crucial factor for electric double-layer capacitors (EDLCs) with solid polymer electrolytes. In this study, the electrolyte solution was made into a viscous solid polymer electrolyte to improve the withstand voltage of the electrolyte. The solid polymer electrolyte was prepared from sodium polyacrylate and doped with potassium hydroxide (KOH) and pure water. Sodium polyacrylate can absorb water at the temperature of 16-28 °C and exhibits suitable ion transfer. The EDLCs consisted of a distilled Japanese shochu-waste-activated-carbon electrode, a titanium mesh collector, and a solid polymer electrolyte. All the processes were performed at room temperature. Their electrochemical characteristics were measured using cyclic voltammetry (CV). From CV, the withstand voltage, cycle range, and specific capacitance were evaluated. The performance of the solid polymer electrolyte varied depending on the weight ratio of the constituent sodium polyacrylate and the molar concentrations of the KOH. Here, the value of molar concentration and its variation, depends on the weight ratio of the material. With the addition of sodium polyacrylate, the withstand voltage, which was 1.2 V, rose to over 2 V. Some of the samples increased up to 5 V. In the cycle measurement, the rate of decrease in capacity exceeded 20% after 250 cycles.

Ionic liquids-based solid polymer electrolytes enhance the battery’s overall performance without drawbacks in safety compared with conventional electrolyte. In order to develop a novel solid electrolyte, we synthesized a series of novel room temperature imidazolium-based polyhedral oligomeric silsesquioxane ionic liquids (POSS-ILs) consisting of POSS-COO− anions and a variety of imidazolium cations, which will be used as plasticizers of solid polymer electrolyte in this work. The thermal stabilities of POSS-ILs have been dramatically enhanced by the introduction of POSS moiety, and the initial decomposition temperatures of POSS-ILs have increased by at least 94 °C compared to their corresponded succinamic acid ionic liquids. The glass transition temperatures of POSS-ILs also have increased to − 15.9 to − 25.4 °C. Then the POSS-ILs are employed to obtain a novel solid polymer electrolyte based on blend of polyethylene oxide, poly(vinylidene fluoride-hexafluoropropylene), propylene carbonate and lithium bis(trifluoromethanesulfonyl) imide with high ionic conductivity and electrochemical windows. The ionic conductivities of POSS-ILs-based solid polymer electrolytes are up to 8.0 × 10−4 S cm−1 at 22 °C and 2.0 × 10−3 S cm−1 at 62 °C, and the electrochemical windows of POSS-ILs-based solid polymer electrolytes are stable up to 5.0 V. Moreover, the Li/LiFePO4 cell containing POSS-ILs-based solid polymer electrolytes exhibits good cycling performance and high rate stability. These results suggest that the POSS-ILs-based solid polymer electrolytes could be a suitable prospective electrolyte material for lithium-ion battery applications.

Currently, electrolytes used in lithium-ion batteries are flammable and leaky, causing safety problems when used under high temperatures or extreme conditions. Solid electrolytes can fundamentally avoid the occurrence of such issues, at the same time, it can significantly increase the energy density of solid state lithium batteries. Solid electrolytes are classified into inorganic solid electrolytes and solid polymer electrolytes. Although inorganic solid electrolytes have the high mechanical strength and room temperature ionic conductivity, it has poor flexibility and complicated preparation process. In contrast, solid polymer electrolyte has good elasticity and good interface contact, which can overcome many disadvantages of the inorganic solid electrolyte. Among them, polyethylene oxide (PEO) is first proposed as a polymer electrolyte. Due to its excellent mechanical properties, electrochemical stability and thermal stability, it has been a hot topic for polymer solid electrolytes for decades. However, its low room temperature ionic conductivity limits practical application. Given the problems existing in PEO-based polymer electrolytes, several methods for improving ionic conductivity have been proposed. The primary methods include plasticization, the organic-inorganic composite, and polymer blending. Comparing these methods, it can be seen that adding plasticizers to the polymer can effectively increase the conductivity of the electrolyte, but at the same time it will cause a decrease in the mechanical properties, and the safety issues limit its application in lithium-ion batteries. Inorganic fillers can balance the problems of ionic conductivity and mechanical properties, but the construction of a good filler-polymer dispersion system is complicated in preparing such composite electrolytes, design a new type of multi-dimensional the ion transport network also face tremendous challenges. Undoubtedly, in the future research, inorganic fillers will be the dominant means in the modification of composite electrolytes. Compared with the former two modification methods, polymer blending is easy to operate and friendly to industry, but low ionic conductivity at room temperature still exist. To give full play to the advantages of polymer blending, using it as an auxiliary means to improve the performance of composite electrolytes will be the primary development direction of such modification methods. PEO is the most widely studied polymer electrolyte. Even though a large number of modification methods have emerged in its development history, the ionic conductivity at room temperature is still limited to a relatively low level. To meet the needs of the application in lithium-ion batteries, a high operating temperature (50−70℃) is still needed, the biggest problem remains exist. To solve the problems in polymer solid electrolytes, the research directions in the future may mainly focus on: Expanding the modification method of PEO to other polymer electrolyte host materials, broadening the scope of research, and finding the available polymer electrolytes at room temperature. Concerned about the preparation of ultra-thin polymer electrolytes, reducing the ion transmission path to increase the transmission efficiency of lithium ions between positive and negative electrodes. Effectively combines inorganic solid electrolytes and solid polymer electrolytes to give full play to their advantages. In addition, exploring the effect of inorganic filler morphology on the conductivity of the composite electrolyte will also deserve attention. Many one-dimensional, two-dimensional materials can build ion transport networks so that lithium ions can travel rapidly along the path. With the deepening of research, it is expected that PEO-based polymer electrolytes may replace liquid electrolytes and become an essential cornerstone for building the next generation of safe and reliable lithium-ion batteries.

Novel PEO-based composite solid electrolytes for All-Solid-State Li-S battery

The ionic conductivity and dielectric properties of the solid nanocomposite polymer electrolytes formed by dispersing a low particle-sized TiO2 ceramic filler in a poly (ethylene oxide) (PEO)-AgNO3 matrix are presented and discussed. The solid nanocomposite polymer electrolytes are prepared by hot press method. The optimum conducting solid polymer electrolyte of polymer PEO and salt AgNO3 is used as host matrix and TiO2 as filler. From the filler concentration-dependent conductivity study, the maximum ionic conductivity at room temperature is obtained for 10 wt% of TiO2. The real part of impedance (Z′) and imaginary part of impedance (Z″) are analyzed using an LCR meter. The dielectric properties of the highest conducting solid polymer electrolyte are analyzed using dielectric permittivity (e′), dielectric loss (e″), loss tangent (tan δ), real part of the electric modulus (M′), and imaginary part of the electric modulus (M″). It is observed that the dielectric constant (e′) increases sharply towards the lower frequencies due to the electrode polarization effect. The maxima of the loss tangent (tan δ) shift towards higher frequencies with increasing temperature. The peaks observed in the imaginary part of the electric modulus (M″) due to conductivity relaxation shows that the material is ionic conductor. The enhancement in ionic conductivity is observed when nanosized TiO2 is added into the solid polymer electrolyte.

Investigating solid polymer and ceramic electrolytes for lithium-ion batteries by means of an extended Distribution of Relaxation Times analysis

The state-of-the-art Li-ion battery has energy density plateauing at ~300 Wh/kg. Replacing the graphite-based anode with Li metal is the easiest way to increase energy density. However, a lithium metal anode is prone to non-uniform plating/striping that leads to capacity decay and dendrite formation. Dendrites trigger short-circuiting and possible explosions as the liquid electrolytes that are used in Li-ion batteries are flammable. Solid-state batteries (SSBs) have the potential to enable Li-metal anodes as they are typically less reactive and nonflammable. Additionally, SSBs exhibit greater mechanical stability and can prevent dendritic growth [1,2]. Furthermore, solid electrolytes show much higher thermal stability, are non-toxic, and have high energy density, making the solid-state battery one of the best choices for the next generation of energy storage devices.Solid polymer electrolytes are an important class of materials for making solid-state batteries commercially viable. These have the potential to increase energy density and decrease contact resistance between anode and separator by formation of a suitable solid-electrolyte-interphase (SEI) [1]. However, this technology still has major hurdles to overcome, like lower Li-ion conductivity when compared to state-of-art ceramic separators. In recent years, garnet-type lithium oxide perovskites have gained attractiveness as state-of-art ceramic separators for SSBs. LLZTO is one such ceramic electrolyte that is being thoroughly investigated by researchers as it shows very high Li-ion conductivity at room temperature [2]. However, these materials suffer from poor interfacial contact. Recently, Yang, et al., [3] combined the best of both worlds with a new type of solid polymer separator which has better physical contact between separator and lithium and good li-ion conductivity at room temperature.In this work, we investigate the transport of Li-ions across both a solid polymer electrolyte and LLZTO solid electrolyte using a symmetric Li-cell configuration. Fig. 1 (a) and (c) show the Li plating/stripping cycling performance in a symmetric cell. The cell voltage measured during plating and stripping is to be very high for LLZTO compared to polymer electrolyte. A possible explanation may be due to high interfacial resistance arising between solid ceramic and lithium metal. Impedance spectroscopy was performed on both LLZTO and polymer separators after each current density step (24 h) and shown in Fig. 1 (b) and (d) respectively. The impedance increased with cycling for the LLZTO separator but decreased with cycling for polymer electrolyte. This may indicate that better interfacial contact between Li and polymer exists and that these connections may become more established while cycling. Furthermore, the transport of Li-ions across the separators will be analyzed using the transference number calculated using the Bruce-Vincent method. The influence of temperature and separator thickness on the transference number will also be used to characterize the nature of ion transport across such solid electrolyte separators. Such deep understanding of the transport mechanism is needed to minimize the different losses in SSBs and make it commercially viable.Figure 1: Li plating/stripping cycling performance of the (a) LLZTO electrolyte, and (c) PEO polymer electrolyte at different current density, with 12 minutes for each plating/stripping half cycle, for a total of 72 h at 70 ℃ temperature and their corresponding impedance are shown in (b) and (d) respectively. References R. Sahore, Z. Du, X. C. Chen, W. B. Hawley, A. S. Westover, and N. J. Dudney, Practical considerations for testing polymer electrolytes for high-energy solid-state batteries, ACS Energy Lett. 2021, 6, 2240-2247.A. Parejiya, R. Amin, M. B. Dixit, R. Essehli, C. J. Jafta, D. L. Wood, III, and I. Belharouak, Improving contact impedance via electrochemical pulses applied to lithium−solid electrolyte interface in solid-state batteries, ACS Energy Lett. 2021, 6, 3669−3675.Yang at al, Copper-coordinated cellulose ion conductors for solid-state batteries, Nature, 2021, 598, 590−596. Figure 1