Electrolytes and Electrolyte/Electrode Interfaces in Sodium‐Ion Batteries: From Scientific Research to Practical Application

Sodium‐ion batteries (SIBs) have drawn considerable interest as power‐storage devices owing to the wide abundance of their constituents and low cost. To realize a high performance–price ratio, the cathode and anode materials must be optimized. As essential components of SIBs, electrolytes should have wide electrochemical windows, high thermal stability, and exceptional ionic conductivity. Therefore, improved electrolytes, based on various materials and compositions, are developed to meet the practical demands of SIBs, including organic electrolytes, ionic liquids, aqueous, solid electrolytes, and hybrid electrolytes. Although mature organic electrolytes are currently used in production, aqueous and solid electrolytes show advantages for future applications, as discussed here in detail. Current efforts in modifying electrolytes to optimize their interfacial compatibility with electrodes, leading to longer battery lifetimes and greater safety, are described. The advanced characterization techniques used to investigate the properties of electrolytes and interfaces are introduced, and the reaction processes and degradation mechanisms of SIBs are revealed. Furthermore, the practical prospects of SIBs promoted by high‐quality electrolytes appropriately matched with electrodes are predicted and directions for developing next‐generation SIBs are suggested.     

Recent achievements on sulfide-type solid electrolytes: crystal structures and electrochemical performance

The all-solid-state lithium batteries using solid electrolytes are considered to be the new generation of devices for energy storage, which might be a key solution for power electric and hybrid electric vehicles in the future. This review focuses on the crystal structures and electrochemical properties of sulfide solid electrolytes. They are classified to several subgroups according to their chemical compositions, namely thiophosphates, halide thiophosphates, sulfide without phosphorus, and glassy sulfides electrolytes, which might be potential solid electrolytes in lithium batteries and may replace the currently used polymeric electrolytes for LIBs. Through discussion, this review provides an insight into future promising sulfide electrolytes.     

Effects of electrolyte on the structure of pyrolytic graphite surfaces in anodic oxidation

Anodic oxidation effects on the structure of the basal and edge surfaces of pyrolytic graphite in alkaline electrolytes have been studied. Laser Raman spectroscopy, a gas-phase chemical modification method, coupled with X-ray photoelectron spectroscopy and secondary ion-mass spectroscopy techniques, were used. Anodic oxidation of the surfaces of pyrolytic graphite in alkaline electrolytes does not cause destruction of their surface structure, even at a higher level of treatment, unlike oxidation of acid electrolytes. In alkaline electrolytes, the number of hydroxyl groups added on the edge surface gradually increases with the increase in treatment level, whereas the number of carboxyl groups does not increase. It was found that anodic oxidation in alkaline electrolytes has a wider permitted range of treatment, in which hydroxyl groups can be added without destroying the edge surface structure, than that found in acid electrolytes. On the other hand, the number of hydroxyl groups added by treating with alkaline electrolytes is smaller than that with acid electrolytes. At a higher treatment level with acid electrolytes, oxidation occurs, even to a depth of 40 nm from the edge surface, whereas with alkaline electrolytes, oxidation occurs only at the surface. On the basis of these results, the effects of electrolytes on the adhesion between carbon fibres and epoxy resin matrix are discussed.     

锂离子电池电解质的最新研究进展

综述了近几年来电解质（即液态电解质和固态电解质）的研究进展，主要是介绍如何提高液态电解质的性能和固态电解质的性能。对液态电解质主要是电化学稳定性的提高，而对固态电解质则包括对离子电导率、电化学稳定、机械性能等的提高。虽然在锂离子电池中，对电池性能起决定作用的是电极材料，但只有对正、负极匹配合适的和性能好的电解质才能达到对锂离子电池性能的优化和提高。因而电解质性能的好坏对锂离子电池的性能有重要的影响。     

Research progress on electrode materials and electrolytes for supercapacitors北大核心CSCD

Supercapacitors have great potential applications for electronic devices, and energy recyling and storage areas owing to their high power density, long cycle life, high safety and excellent performance at low temperatures. The electrode materials and electrolytes are two key factors that influence their performance. The electrode materials used in supercapacitors include carbon materials such as activated carbons, carbon nanotubes, graphene, carbon nanofibers and carbon nano-onions, metal oxides, conductive polymers and their composites. The electrolytes are aqueous electrolytes, organic electrolytes or ionic liquids. Here research progress on the electrode materials and liquid electrolytes for supercapacitors is summarized, their advantages and disadvantages are analyzed, and new electrode materials and electrolytes are suggested.     

Conductivity behaviour of polymer gel electrolytes: Role of polymer

Polymer is an important constituent of polymer gel electrolytes along with salt and solvent. The salt provides ions for conduction and the solvent helps in the dissolution of the salt and also provides the medium for ion conduction. Although the polymer added provides mechanical stability to the electrolytes yet its effect on the conductivity behaviour of gel electrolytes as well as the interaction of polymer with salt and solvent has not been conclusively established. The conductivity of lithium ion conducting polymer gel electrolytes decreases with the addition of polymer whereas in the case of proton conducting polymer gel electrolytes an increase in conductivity has been observed with polymer addition. This has been explained to be due to the role of polymer in increasing viscosity and carrier concentration in these gel electrolytes.     

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。     

低聚醚/聚氨酯固体电解质的形态及离子导电性能

采用聚氧化乙烯或聚二氧戊环作为增塑剂对分别以聚四氢呋喃（PTHF）和聚己二酸乙二醇酯（EGEGPU）为软段的聚氨酯固体电解质体系进行了共混增塑，并对所得固体电解质体系的形态和离子导电性能进行了讨论，结果表明，低聚醚可以作为增塑剂而有效地改善聚氨酯固体电解质体系的链段柔顺性及聚集形态，从而提高体系的离子导电性能，PEG可以对EGPU固体电解质体系进行有效的增塑改性，其中EGPU132－PEG600－12的离子电导率在室温下可以达到10^-5S/cm以上；PDXL对EGPU固体电解质增塑改性效果较差，但是PDXL是PTHFPU固体电解质体系的有效的增塑剂。     

Lithium-Ion Battery Separators for Ionic-Liquid Electrolytes: A Review

Ionic liquids (ILs) are widely studied as a safer alternative electrolyte for lithium-ion batteries. The properties of IL electrolytes compared to conventional electrolytes make them more thermally stable, but they also have poor wetting with commercial separators. In a lithium-ion battery, the electrolyte should completely wet out the separator and electrodes to reduce the cell internal resistance. Investigations of cell materials with IL electrolytes have shown that the wetting issues in IL–electrolyte cells are most likely due to poor separator compatibility, not electrode compatibility. A compatible separator must be developed before IL electrolytes can be used in commercial lithium-ion batteries. Herein, separators for IL electrolytes, including commercial and novel separators, are reviewed. Separators with different processing methods, polymers, additives, and different IL electrolytes are considered. Collated, the separator studies show a strong correlation between ionic conductivity and membrane porosity, even more than the electrolyte type. The challenge of a suitable separator for IL electrolytes is not solved yet. Herein, it is revealed that a separator for IL electrolytes will most likely require a combination of high thermal and mechanical stability polymer, ceramic additives, and an optimized manufacturing process.     

锂离子电池玻璃态电解质导电机理的研究进展

锂离子电池玻璃态电解质同晶体型电解质相比较具有导电性各向同性、锂离子电导率高等诸多优点, 开发在室温下具有较高的离子电导率及良好的化学、电化学稳定性的玻璃态电解质材料已经成为锂离子电池领域的重要研究方向之一。本文介绍了各种玻璃态电解质体系的导电特性及导电机理, 并重点分析与讨论混合网络形成体效应在一些典型玻璃态电解质体系中的微观作用机理。本文还总结了混合网络形成体效应在玻璃态电解质中发生的前提条件, 并指出深入研究玻璃态电解质的导电机理对开发出具有优异电化学性能的无机非晶固态电解质体系具有重要的指导意义。     

Nacre-Inspired Composite Electrolytes for Load-Bearing Solid-State Lithium-Metal Batteries

Solid-state lithium-metal batteries with solid electrolytes are promising for next-generation energy-storage devices. However, it remains challenging to develop solid electrolytes that are both mechanically robust and strong against external mechanical load, due to the brittleness of ceramic electrolytes and the softness of polymer electrolytes. Herein, a nacre-inspired design of ceramic/polymer solid composite electrolytes with a “brick-and-mortar” microstructure is proposed. The nacre-like ceramic/polymer electrolyte (NCPE) simultaneously possesses a much higher fracture strain (1.1%) than pure ceramic electrolytes (0.13%) and a much larger ultimate flexural modulus (7.8 GPa) than pure polymer electrolytes (20 MPa). The electrochemical performance of NCPE is also much better than pure ceramic or polymer electrolytes, especially under mechanical load. A 5 × 5 cm² pouch cell with LAGP/poly(ether-acrylate) NCPE exhibits stable cycling with a capacity retention of 95.6% over 100 cycles at room temperature, even undergoes a large point load of 10 N. In contrast, cells based on pure ceramic and pure polymer electrolyte show poor cycle life. The NCPE provides a new design for solid composite electrolyte and opens up new possibilities for future solid-state lithium-metal batteries and structural energy storage.     

超级电容器电解质研究进展

电解质作为超级电容器的重要组成部分,对器件性能起着关键性作用。本文对近些年来超级电容器各种电解质,包括水系、有机液体、离子液体、固态/准固态聚合物电解质和氧化还原体系电解质的特点和最新研究成果进行了描述;重点介绍了固态/准固态聚合物电解质的分类及其性能研究概况。提出了发展电位窗口宽、离子电导率高、电化学性能稳定的离子液体和机械强度等综合性能优良的凝胶聚合物电解质是将来超级电容器电解质发展领域的趋势,最后对超级电容器电解质的发展前景进行了展望。     

High ion conducting polymer nanocomposite electrolytes using hybrid nanofillers

There is a growing shift from liquid electrolytes toward solid polymer electrolytes, in energy storage devices, due to the many advantages of the latter such as enhanced safety, flexibility, and manufacturability. The main issue with polymer electrolytes is their lower ionic conductivity compared to that of liquid electrolytes. Nanoscale fillers such as silica and alumina nanoparticles are known to enhance the ionic conductivity of polymer electrolytes. Although carbon nanotubes have been used as fillers for polymers in various applications, they have not yet been used in polymer electrolytes as they are conductive and can pose the risk of electrical shorting. In this study, we show that nanotubes can be packaged within insulating clay layers to form effective 3D nanofillers. We show that such hybrid nanofillers increase the lithium ion conductivity of PEO electrolyte by almost 2 orders of magnitude. Furthermore, significant improvement in mechanical properties were observed where only 5 wt % addition of the filler led to 160% increase in the tensile strength of the polymer. This new approach of embedding conducting-insulating hybrid nanofillers could lead to the development of a new generation of polymer nanocomposite electrolytes with high ion conductivity and improved mechanical properties.     

Advanced Composite Solid Electrolytes for Lithium Batteries: Filler Dimensional Design and Ion Path Optimization

Composite solid electrolytes are considered to be the crucial components of all-solid-state lithium batteries, which are viewed as the next-generation energy storage devices for high energy density and long working life. Numerous studies have shown that fillers in composite solid electrolytes can effectively improve the ion-transport behavior, the essence of which lies in the optimization of the ion-transport path in the electrolyte. The performance is closely related to the structure of the fillers and the interaction between fillers and other electrolyte components including polymer matrices and lithium salts. In this review, the dimensional design of fillers in advanced composite solid electrolytes involving 0D–2D nanofillers, and 3D continuous frameworks are focused on. The ion-transport mechanism and the interaction between fillers and other electrolyte components are highlighted. In addition, sandwich-structured composite solid electrolytes with fillers are also discussed. Strategies for the design of composite solid electrolytes with high room temperature ionic conductivity are summarized, aiming to assist target-oriented research for high-performance composite solid electrolytes.     

Molecular Dynamics Analysis of High-temperature Molten-salt Electrolytes in Thermal Batteries

The purpose of this research is to improve the discharge rate and to predict the melting point of high-temperature molten-salt electrolytes in thermal batteries. Using molecular dynamics (MD) simulation techniques, we tried to develop some novel ternary and quaternary molten electrolytes to replace conventional binary LiCl-KCl ones. The simulation results with greater ionic conductivity and lower melting point are consistent with experimental results reported by previous literatures. The MD results have found that the lithium ion mole fraction in the molten-salt electrolytes affects the ionic conductivity significantly. This paper demonstrates that MD simulation techniques are a useful tool to screen various design ideas on the multi-component electrolytes in a more efficient way. The molecular composition of each component of the molten-salt electrolytes can be optimized using this atomistic analysis instead of trial-and-error experiments.     

聚合物固态电解质的研究进展

固态储能器件由于其在安全性和潜在的高能量密度方面的优势,被认为是下一代能量存储设备。固态电解质作为固态储能器件的关键元件,具有高的安全系数,近年来受到了广泛的关注。其中聚合物固态电解质由于其制备简便,价格低廉且界面相容性好等优点,成为固态电解质的重要组成部分。文中从聚合物的微观结构和聚合物固态电解质的宏观形态出发,分别概述了聚环氧乙烷(PEO)、聚碳酸酯(PC)、聚硅氧烷和其他聚合物基固态电解质的传输机理及在各领域的发展与应用,并对聚合物固态电解质未来的发展进行展望。     

锂离子电池聚合物电解质研究进展

综述了二次锂离子电池聚合物电解质的最新研究进展,对不同类型的聚合物电解质按其基体进行分类,包括常见的几种聚合物基体以及近年来发展起来的几种新型聚合物基体。对于每类基体相关的研究成果,主要关注的是电化学性能。对一些性能优异的聚合物电解质体系及其相应的制备方法,给出了较为全面的概述。与使用液体有机电解质的二次锂离子电池相比...     

金属锆微弧氧化电解液体系和氧化时问对陶瓷膜层的影响

分别用钨酸钠、偏铝酸钠、硅酸钠电解液体系在金属锆表面上制备了氧化锆陶瓷膜。探讨了电解液种类、氧化时间对膜层相结构、微观形貌和耐蚀性的影响。结果表明：氧化膜成分、组织结构、形貌和耐蚀性受电解液种类影响较大;钨酸钠、偏铝酸钠体系陶瓷膜由单斜相组成,而硅酸钠体系则形成了异常的正交相及单斜相,其膜层的耐蚀性不同程度地优于钨酸钠...     

聚合物电解质离子电导率的影响因素

聚合物电解质具有质轻、粘弹性好、优良的安全性能和加工性能等许多无机电解质和有机溶剂电解质所不可比拟的优点，在微型移动电源领域有着广泛的应用前景。但由于室温电导率低，应用受到限制。综述了聚合物电解质的离子传导机制以及室温电导率的影响因素。     

Influence of supporting electrolytes on the rate of deposition of γ-FeOOH from Fe2+ ions

Simple uni-univalent electrolytes introduce significant modifications in the rate of formation of γ-FeOOH from Fe²⁺. Kinetic results show that the electrolytes only influence the partition reaction of Fe²⁺ at the oxide-solution interface. The effect is induced by specific interactions between the oxide and the anions of the electrolytes.