Polymer electrolyte based dye-sensitized solar cell with rice starch and 1-methyl-3-propylimidazolium iodide ionic liquid

Biodegradable rice starch was used to prepare solid polymer electrolytes (SPEs) using sodium iodide salt. The polymer electrolytes are prepared using solution cast technique. 1-methyl-3-propylimidazolium iodide (MPII) ionic liquid was incorporated in the polymer electrolyte. The ionic conductivity of SPEs are measured and temperature-dependent behavior of SPEs studied. All the solid polymer electrolytes follow Arrhenius type of thermal activated model. The ionic conductivity increased after addition of MPII ionic liquid. The highest ionic conductivity of 1.20 × 10^− 3 S cm^− 1 is achieved upon addition of 20 wt.% of MPII ionic liquid. Structural properties of polymer electrolytes are studied with FTIR and XRD which confirmed complexation between polymer and ionic liquid. The polymer electrolytes are analyzed for thermal study using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Dye-sensitized solar cells (DSSC) are fabricated using polymer electrolytes and studied under Sun simulator. The highest energy conversion efficiency of 2.09% is attained after addition of 20 wt.% of MPII ionic liquid.     

Aliphatic Polycarbonate‐Based Solid‐State Polymer Electrolytes for Advanced Lithium Batteries: Advances and Perspective

Conventional liquid electrolytes based lithium‐ion batteries (LIBs) might suffer from serious safety hazards. Solid‐state polymer electrolytes (SPEs) are very promising candidate with high security for advanced LIBs. However, the quintessential frailties of pristine polyethylene oxide/lithium salts SPEs are poor ionic conductivity (≈10⁻⁸ S cm⁻¹) at 25 °C and narrow electrochemical window (<4 V). Many innovative researches are carried out to enhance their lithium‐ion conductivity (10⁻⁴ S cm⁻¹ at 25 °C), which is still far from meeting the needs of high‐performance power LIBs at ambient temperature. Therefore, it is a pressing urgency of exploring novel polymer host materials for advanced SPEs aimed to develop high‐performance solid lithium batteries. Aliphatic polycarbonate, an emerging and promising solid polymer electrolyte, has attracted much attention of academia and industry. The amorphous structure, flexible chain segments, and high dielectric constant endow this class of polymer electrolyte excellent comprehensive performance especially in ionic conductivity, electrochemical stability, and thermally dimensional stability. To date, many types of aliphatic polycarbonate solid polymer electrolyte are discovered. Herein, the latest developments on aliphatic polycarbonate SPEs for solid‐state lithium batteries are summarized. Finally, main challenges and perspective of aliphatic polycarbonate solid polymer electrolytes are illustrated at the end of this review.     

聚合物复合固体电解质材料研究进展

固体电解质是发展高安全、高能量密度全固态锂电池的重要材料基础。由聚合物相与无机相复合形成的聚合物复合固体电解质,兼具聚合物轻质、柔性,以及无机材料高强度、高稳定性等优势,是最具应用潜力的固体电解质材料。目前,制约聚合物复合固体电解质实际应用的主要瓶颈问题为其室温离子电导率较低。综述了目前关于聚合物复合固体电解质离子传导机制的科学认识以及提升其离子电导率的方法,分析了先进表征工具在揭示聚合物复合固体电解质离子传导机制方面的应用潜力,并展望了聚合物复合固体电解质未来的发展方向和工作重点。     

Electrochemical properties of composite electrolytes based on poly(ethylene oxide)/poly(ethylene imine) containing the inorganic silica fillers

In this study, poly(ethylene oxide) (PEO) and poly(ethylene imine) (PEI) polymer blends containing inorganic silica fillers were studied in order to enhance the ion conductivity and interfacial properties. Lithium perchlorate (LiCIO4) as a salt, and silica (SiO2) as the inorganic filler were introduced in the polymer electrolyte composites and were examined to evaluate their use to improve the ionic conductivity. The addition of inorganic fillers in polymer electrolytes has resulted in high ionic conductivity at a room temperature. The structure and morphology of the solid polymer electrolytes were evaluated using X-ray diffraction (XRD) and scanning electron microscope (SEM). The ionic conductivity was measured by an AC impedance method. The enhanced conductivity was dependent on the decreased crystallinity and more heterogeneous morphologies.     

固态锂电池用MOF/聚氧化乙烯复合聚合物电解质

固态聚合物电解质具有柔韧性好和易于加工的优势, 可制备各种形状的固态锂电池, 杜绝漏液问题。但固态聚合物电解质存在离子电导率低以及对锂金属负极不稳定等问题。本研究以纳米金属-有机框架材料UiO-66为聚合物电解质的填料, 用于改善电解质的性能。UiO-66与聚氧化乙烯(poly(ethylene oxide), PEO)链上醚基的氧原子的配位作用以及与锂盐中阴离子的相互作用, 可显著提高聚合物电解质的离子电导率(25 ℃, 3.0×10 ^-5S/cm; 60 ℃, 5.8×10 ^-4 S/cm), 并将锂离子迁移数提高至0.36, 电化学窗口拓宽至4.9 V。此外, 制备的PEO基固态电解质对金属锂具有良好的稳定性, 对称电池在60 ℃、0.15 mA·cm ^-2电流密度下可稳定循环1000 h, 锂电池的电化学性能得到显著改善。     

Perovskite‐type Li‐ion solid electrolytes: a review

All-solid-state lithium batteries with inorganic solid electrolytes are recognized as the next-generation battery systems due to their high safety and energy density. To realize the practical applications of all-solid-state lithium battery, it is essential to develop solid electrolytes which exhibit high Li-ion conductivity, low electron conductivity, wide electrochemical window, and low interface resistance between the electrode and the solid electrolyte. Among many solid electrolytes, the perovskite-type lithium-ion solid electrolytes are promising candidates that can be applied to all-solid-state lithium batteries. However, the perovskite-type solid electrolytes still suffer from several significant problems, such as poor stability against lithium metal, high interface resistance, etc. In this review, we have analyzed and summarized the properties of perovskite-type solid electrolytes with two different systems, namely three-component oxide system Li_3xLa_2/3?xTiO₃ (LLTO) and four-component oxide system (Li, Sr)(B, B’)O₃ (B?=?Zr, Hf, Ti, Sn, Ga, etc., B’ = Nb, Ta, etc.). LLTO and (Li, Sr)(B, Ta)O₃ compounds exhibit high Li-ion conductivity of up to >?10^??4 S·cm^??1 at room temperature. Based on the review of academic literature, the ion transportation mechanism, composition design, electrical properties, stability, doping, and application of these solid electrolytes are discussed, which would be helpful for the further development of all-solid-state lithium batteries.

     

PAN–PEO solid polymer electrolytes with high ionic conductivity

The transparent and flexible solid polymer electrolytes (SPEs) are fabricated from polyacrylonitrile–polyethylene oxide (PAN–PEO) copolymer. The formation of the copolymer is confirmed by Fourier-transform infrared spectroscopy (FTIR) and Gel permeation chromatography (GPC) measurements. The effects of acrylonitrile (AN) wt% content and M_n(PEO) on ionic conductivity are investigated by alternating current (ac) impedance spectroscopy. By controlling and adjusting the AN wt% content and doping PEO with high molecular weight, the ionic conductivity of SPEs is optimized. The ionic conductivity of PAN–PEO solid polymer electrolytes is found to be high 6.79 × 10⁻⁴ S cm⁻¹ at 25 °C with an [EO]/[Li] ratio of about 10, and are electrochemically stable up to about 4.8 V versus Li/Li⁺. The conductivity and interfacial resistance remain almost constant even at 80 °C.     

A Flexible Ceramic/Polymer Hybrid Solid Electrolyte for Solid-State Lithium Metal Batteries

Ceramic/polymer hybrid solid electrolytes (HSEs) have attracted worldwide attentions because they can overcome defects by combining the advantages of ceramic electrolytes (CEs) and solid polymer electrolytes (SPEs). However, the interface compatibility of CEs and SPEs in HSE limits their full function to a great extent. Herein, a flexible ceramic/polymer HSE is prepared via in situ coupling reaction. Ceramic and polymer are closely combined by strong chemical bonds, thus the problem of interface compatibility is resolved and the ions can transport rapidly by an expressway. The as-prepared membrane demonstrates an ionic conductivity of 9.83 × 10⁻⁴ S cm⁻¹ at room temperature and a high Li⁺ transference numbers of 0.68. This in situ coupling reaction method provides an effective way to resolve the problem of interface compatibility.     

Computer Modeling of Ionic Conductivity in Low Temperature Doped Ceria Solid Electrolytes

Solid oxides, such as ceria (CeO₂) doped with cations of lower valance, are potential electrolytes for future solid oxide fuel cells. This is due to the theoretically high ionic conductivity at low operation temperature. This paper investigates the feasibility of two potential electrolytes which are samarium-doped ceria (SDC) and gadolinium-doped ceria (GDC) to replace the traditional yttria-stablized zirconia (YSZ). Molecular simulation techniques were employed to study the influence of different dopant concentrations at different operation temperatures on the ionic conductivity from the atomistic perspective. Simulation results show that the optimized ionic conductivity occurs at 11.11mol% concentration using both dopants of Gd₂O₃ and Sm₂O₃. The temperature effect was also examined under a fixed concentration simulation to check how low temperature they still function. The predicted ionic conductivities have been verified with published experimental results and show reasonable agreements. This simulation technique reveals a clear picture with qualitative and quantitative connection between the choice of the dopant and the improvement of the ionic conductivity of fuel cell electrolytes.     

Effects of preparation methods on structure,ionic conductivity and dielectric relaxation of solid polymeric electrolytes

The solid polymer electrolytes (SPEs) consisted of poly(ethylene oxide) (PEO) and lithium perchlorate (LiClO₄) (PEO₂₀–LiClO₄ and PEO₈–LiClO₄ electrolytes of composition stoichiometric ratios EO:Li⁺ = 20:1 and 8:1) have been prepared by various blending methods. The simple solution casting, solution–cast hot pressed, dry blended melt pressed, high intensity ultrasonic assisted, microwave irradiated, and both the ultrasonicated and microwave irradiated solution–cast followed by their remelt with hot pressed methods have been used for preparation of the SPEs films. The complex formation between etheric oxygen (EO) of PEO and cation (Li⁺) of LiClO₄ is confirmed by relative changes in amorphous phase of these electrolytes which is investigated by X-ray diffraction measurements. It is found that the amount of amorphous phase of these SPEs is strongly influenced by their preparation methods and the salt concentration. The complex dielectric function, ac electric conductivity, electric modulus and impedance spectra of the electrolytes are studied over the frequency range of 20 Hz to 1 MHz by dielectric relaxation spectroscopy at ambient temperature. The dc ionic conductivity of PEO₈–LiClO₄ electrolytes is found two to three orders of magnitude higher than that of the PEO₂₀–LiClO₄ electrolytes, which is significantly affected by their preparation methods. The cations coupled PEO chain segmental dynamics and its correlation with the ionic conductivity of these electrolytes has been explored by considering the values of relaxation times and dielectric relaxation strength. Results reveal that the ionic conductivity of PEO₈–LiClO₄ electrolytes can be tuned over two orders of magnitude by adopting different blending methods with a state-of-the-art engineering.     

Enhancement of ionic conductivity of PEO based polymer electrolyte by the addition of nanosize ceramic powders

The ionic conductivity of polyethylene oxide (PEO) based solid polymer electrolytes (SPEs) has been improved by the addition of nanosize ceramic powders (TiO2 and AL2O3). The PEO based solid polymer electrolytes were prepared by the solution-casting method. Electrochemical measurement shows that the 10 wt% TiO2 PEO-LiClO4 polymer electrolyte has the best ionic conductivity (about 10(-4) S cm(-1) at 40-60 degrees C). The lithium transference number of the 10 wt% TiO2 PEO-LiClO4 polymer electrolyte was measured to be 0.47, which is much higher than that of bare PEO polymer electrolyte. Ac impedance testing shows that the interface resistance of ceramic-added PEO polymer electrolyte is stable. Linear sweep voltammetry measurement shows that the PEO polymer electrolytes are electrochemically stable in the voltage range of 2.0-5.0 V versus a Li/Li+ reference electrode.     

Li‐Ion Cooperative Migration and Oxy‐Sulfide Synergistic Effect in Li14P2Ge2S16−6xOx Solid‐State‐Electrolyte Enables Extraordinary Conductivity and High Stability

Critical to the development of all‐solid‐state lithium‐ion batteries technology are novel solid‐state electrolytes with high ionic conductivity and robust stability under inorganic solid‐electrolyte operating conditions. Herein, by using density functional theory and molecular dynamics, a mixed oxygen‐sulfur‐based Li‐superionic conductor is screened out from the local chemical structure of β‐Li₃PS₄ to discover novel Li₁₄P₂Ge₂S₈O₈ (LPGSO) with high ionic conductivity and high stability under thermal, moist, and electrochemical conditions, which causes oxygenation at specific sites to improve the stability and selective sulfuration to provide an O‐S mixed path by Li‐S/O structure units with coordination number between 3 and 4 for fast Li‐cooperative conduction. Furthermore, LPGSO exhibits a quasi‐isotropic 3D Li‐ion cooperative diffusion with a lesser migration barrier (≈0.19 eV) compared to its sulfide‐analog Li₁₄P₂Ge₂S₁₆. The theoretical ionic conductivity of this conductor at room temperature is as high as ≈30.0 mS cm^?1, which is among the best in current solid‐state electrolytes. Such an oxy‐sulfide synergistic effect and Li‐ion cooperative migration mechanism would enable the engineering of next‐generation electrolyte materials with desirable safety and high ionic conductivity, for possible application in the near future.     

The Sand equation and its enormous practical relevance for solid-state lithium metal batteries

In this work, different Li salt concentrations and ionic conductivities of poly(ethylene oxide)-based solid polymer electrolytes (PEO-based SPEs) are correlated with the performance of LiNi_0.6Mn_0.2Co_0.2O₂ (NMC622)||Li full cells. While the SPEs with different salt concentrations behave similarly in NMC622||Li cells at 60 °C, their influence on the specific capacities is significant at 40 °C. Below a distinct salt concentration, i.e. > 20:1 (EO:Li), a sudden blocking-type polarization appears, indicatable by an almost vertical voltage profile, both in full and in Li||Li symmetric cells. The corresponding time and current density for this polarization-type is shown to mathematically fit with the Sand equation, which subsequently allows calculation of D_Li⁺. According this relation, lack of Li⁺ in the electrolyte close to the electrode surface can be concluded to be the origin of this polarization, but is shown to appear only for “kinetically limiting” conditions e.g. above a threshold current density, above a threshold SPE thickness and/or below a threshold salt concentration (ionic conductivity), i.e. at mass transfer limiting conditions. With the support of this relation, maximal applicable current densities and/or SPE thicknesses can be calculated and predicted for SPEs.     

Achieving Ultra-Stable All-Solid-State Sodium Metal Batteries with Anion-Trapping 3D Fiber Network Enhanced Polymer Electrolyte

All-solid-state sodium metal batteries paired with solid polymer electrolytes (SPEs) are considered a promising candidate for high energy-density, low-cost, and high-safety energy storage systems. However, the low ionic conductivity and inferior interfacial stability with Na metal anode of SPEs severely hinder their practical applications. Herein, an anion-trapping 3D fiber network enhanced polymer electrolyte (ATFPE) is developed by infusing poly(ethylene oxide) matrix into an electrostatic spun fiber framework loading with an orderly arranged metal-organic framework (MOF). The 3D continuous channel provides a fast Na⁺ transport path leading to high ionic conductivity, and simultaneously the rich coordinated unsaturated cation sites exposed on MOF can effectively trap anions, thus regulating Na⁺ concentration distribution for constructing stable electrolyte/Na anode interface. Based on such advantages, the ATFPE exhibits high ionic conductivity and considerable Na⁺ transference number, as well as enhanced interfacial stability. Consequently, Na/Na symmetric cells using this ATFPE possess cyclability over 600 h at 0.1 mA cm⁻² without discernable Na dendrites. Cooperated with Na₃V₂(PO₄)₃ cathode, the all-solid-state sodium metal batteries (ASSMBs) demonstrate significantly improved rate and cycle performances, delivering a high discharge capacity of 117.5 mAh g⁻¹ under 0.1 C and rendering high capacity retention of 78.2% after 1000 cycles even at 1 C.     

Electrochemical performance of poly(vinyl alcohol)-based solid polymer electrolyte for lithium polymer batteries

Solid polymer electrolytes (SPEs) are an excellent alternative to liquid electrolytes due to their non-volatility, low toxicity, and high energy density. In this study, a SPE having the ion transport mechanism decoupled from segmental motion of a polymer based on poly(vinyl alcohol) (PVA) containing the salt lithium trifluoromethane sulfonate (LiCF3SO3, LiTf) has been prepared to overcome the low ionic conductivity of traditional SPEs at room temperature. PVA has a high glass transition temperature (358 K) and good mechanical properties, and despite being atactic, it can crystallize, especially if highly hydrolyzed. From an ac impedance analysis, it was found that the ionic conductivity of the PVA-based SPE increased with increasing salt concentration. In particular, a dramatic increase was observed between 40 and 50 wt% of salt. The ionic conduction mechanism of the PVA-based SPE is proposed based on intensive study using FT-IR spectroscopic measurements, XRD and AFM. Through measurements of linear sweep voltammetry (LSV) and cyclic voltammetry (CV), it is also found that the SPE with PVA and LiCF3SO3 has good electrochemical stability.     

Revealing Structural Insights of Solid Electrolyte Interphase in High-Concentrated Non-Flammable Electrolyte for Li Metal Batteries by Cryo-TEM

High-concentrated non-flammable electrolytes (HCNFE) in lithium metal batteries prevent thermal runaway accidents, but the microstructure of their solid electrolyte interphase (SEI) remains largely unexplored, due to the lack of direct imaging tools. Herein, cryo-HRTEM is applied to directly visualize the native state of SEI at the atomic scale. In HCNFE, SEI has a uniform laminated crystalline-amorphous structure that can prevent further reaction between the electrolyte and lithium. The inorganic SEI component, Li₂S₂O₇, is precisely identified by cryo-HRTEM. Density functional theory (DFT) calculations demonstrate that the final Li₂S₂O₇ phase has suitable natural transmission channels for Li-ion diffusion and excellent ionic conductivity of 1.2 × 10^-5 S cm^-1.     

Electrochemical properties of solid polymer electrolytes prepared by the hard/soft acid base principle

In order to improve the electrochemical properties including ionic conductivity of SPEs (solid polymer electrolytes), understanding of the interaction between the polymer and salt in the SPE is important. In this study, four types of polymer matrices and four types of salts were used according to the hard/soft acid base (HSAB) principle. The results of impedance measurement reveal that the ionic conductivities are affected by the HSAB principle at low salt concentration. With increasing salt content, however, the SPEs are influenced by the ion hopping property of salt rather than by the solubility of the polymer with salt. In contrast, the PPS-based SPE shows different characteristics because it is prepared as a slurry phase at high salt content.     

A Single-Ion Conducting Borate Network Polymer as a Viable Quasi-Solid Electrolyte for Lithium Metal Batteries

Lithium-ion batteries have remained a state-of-the-art electrochemical energy storage technology for decades now, but their energy densities are limited by electrode materials and conventional liquid electrolytes can pose significant safety concerns. Lithium metal batteries featuring Li metal anodes, solid polymer electrolytes, and high-voltage cathodes represent promising candidates for next-generation devices exhibiting improved power and safety, but such solid polymer electrolytes generally do not exhibit the required excellent electrochemical properties and thermal stability in tandem. Here, an interpenetrating network polymer with weakly coordinating anion nodes that functions as a high-performing single-ion conducting electrolyte in the presence of minimal plasticizer, with a wide electrochemical stability window, a high room-temperature conductivity of 1.5 × 10⁻⁴ S cm⁻¹, and exceptional selectivity for Li-ion conduction (t_Li+ = 0.95) is reported. Importantly, this material is also flame retardant and highly stable in contact with lithium metal. Significantly, a lithium metal battery prototype containing this quasi-solid electrolyte is shown to outperform a conventional battery featuring a polymer electrolyte.     

The effects of salt concentration on ion state and conductivity in comb cross-linked polymer electrolytes

A new type of comb cross-linked polyurethane/acrylate polymer was designed. The polymer has sparse network structure with many long comb molecule chains. A new solid polymer electrolyte (SPE) was prepared based on the polymer. The salt in the solid polymer electrolytes has different existent states with different salt contents. With increase of salt concentration, the ion pairing gradually becomes important existent form of salt, and T _g value of the SPE increases. At the same time, ionic conductivity increases rapidly. It is possible to design novel solid polymer electrolytes with high ionic conductivity to meet practical application by comb cross-linked polymer with high salt content.     

Thiol-Branched Solid Polymer Electrolyte Featuring High Strength,Toughness, and Lithium Ionic Conductivity for Lithium-Metal Batteries

Lithium-metal batteries (LMBs) with high energy densities are highly desirable for energy storage, but generally suffer from dendrite growth and side reactions in liquid electrolytes; thus the need for solid electrolytes with high mechanical strength, ionic conductivity, and compatible interface arises. Herein, a thiol-branched solid polymer electrolyte (SPE) is introduced featuring high Li⁺ conductivity (2.26 × 10⁻⁴ S cm⁻¹ at room temperature) and good mechanical strength (9.4 MPa)/toughness (≈500%), thus unblocking the tradeoff between ionic conductivity and mechanical robustness in polymer electrolytes. The SPE (denoted as M-S-PEGDA) is fabricated by covalently cross-linking metal–organic frameworks (MOFs), tetrakis (3-mercaptopropionic acid) pentaerythritol (PETMP), and poly(ethylene glycol) diacrylate (PEGDA) via multiple C S C bonds. The SPE also exhibits a high electrochemical window (>5.4 V), low interfacial impedance (<550 Ω), and impressive Li⁺ transference number (t_Li+ = 0.44). As a result, Li||Li symmetrical cells with the thiol-branched SPE displayed a high stability in a >1300 h cycling test. Moreover, a Li|M-S-PEGDA|LiFePO₄ full cell demonstrates discharge capacity of 143.7 mAh g⁻¹ and maintains 85.6% after 500 cycles at 0.5 C, displaying one of the most outstanding performances for SPEs to date.