Li2S-P2S5体系电解质及其在全固态锂离子电池中的应用研究进展

全固态锂离子电池具有安全性能好、能量密度高、工作温区广等优点,被广泛应用于便携式电子设备。固态电解质是全固态锂离子电池的关键材料之一,其中的硫化物电解质具有离子电导率高、电化学窗口宽、晶界电阻低和易成膜等特点,被认为最有希望应用于全固态锂离子电池。本文综述了Li_2S-P_2S_5体系电解质的发展状况,包括固态电解质的制备、改性、表征以及电极/固态电解质之间的固-固界面的稳定兼容问题。本文还涉及了以Li_2S-P_2S_5为电解质的全固态锂离子电池性能的研究进展。     

Challenges and Development of Composite Solid Electrolytes for All-solid-state Lithium Batteries

All-solid-state lithium batteries are considered to be a new battery system with great development potential and application prospects due to the advantages of high energy density and high security.As a key component of all-solid-state lithium batteries,the development of solid-state electrolytes has received extensive attention in recent years,but most solid electrolytes still exhibit problems,such as low ion conductivity and poor interface compatibility.The design of composite solid-state electrolyte materials with both excellent electrochemical and mechanical properties is an effective way to develop all-solid-state lithium batteries.This review introduces different types of pure component solid electrolytes and analyzes their respective advantages and characteristics firstly.Furthermore,the research progress of composite electrolytes in preparation method,ionic conduction,suppression of lithium dendrites,and the improvement of electrochemical performances are reviewed from the perspective of composite electrolyte structure design,which is to meet different performance requirements.And the future development direction and trend of composite electrolytes are prospected.     

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.     

Li7P3S11电解质的合成、传导及应用

固态电解质是固态电池中的关键材料,开发具有高离子电导率、高化学/电化学稳定性、电极兼容性良好的固态电解质正成为研究热点。硫化物固态电解质相较其它固态电解质具有更高的离子电导率和良好的机械加工性能等优势,是最有前景实现实用化的固态电解质之一。在众多硫化物固态电解质中,Li₇P₃S₁₁因其高的离子电导率和较低的原料成本而极具研究意义。本文首先介绍了Li₇P₃S₁₁电解质的结构、Li+传导机理及合成路径;其次,针对该电解质的电导率提高、空气/水稳定性提升、固固界面稳定性及电解质自身稳定性改善等问题,综述了目前常用的改性策略研究;再次,总结了基于Li₇P₃S₁₁电解质的全固态锂离子电池和全固态锂硫电池的构筑;最后,本文分析了Li₇P₃S₁₁电解质的研究和应用面临的挑战,并指出该电解质未来发展的趋势。     

高性能硫化物基全固态锂电池设计：从实验室到实用化

全固态锂电池因其优异的安全性和高能量密度成为储能领域的重点研究内容。硫化物电解质因其高离子电导率、良好电极/电解质界面兼容性及易加工性,有力推动了硫化物基全固态锂电池的发展。本文首先从实验室研究阶段出发,从正极/电解质界面、硫化物电解质自身及负极/电解质界面三方面阐述了硫化物基全固态锂电池现阶段面临的主要问题,并介绍了相关的解决策略。随后从硫化物基全固态锂电池的实用化生产角度出发,介绍了电极/电解质膜的制膜工艺、软包电池的装配相关问题、高载正极的设计及硫化物电解质的大规模、低成本制备。最后展望了硫化物基全固态锂电池的未来研究方向和发展趋势。     

Materials Design Principles for Air-Stable Lithium/Sodium Solid Electrolytes

Sulfide solid electrolytes are promising inorganic solid electrolytes for all-solid-state batteries. Despite their high ionic conductivity and desirable mechanical properties, many known sulfide solid electrolytes exhibit poor air stability. The spontaneous hydrolysis reactions of sulfides with moisture in air lead to the release of toxic hydrogen sulfide and materials degradation, hindering large-scale manufacturing and applications of sulfide-based solid-state batteries. In this work, we systematically investigate the hydrolysis and reduction reactions in Li- and Na-containing sulfides and chlorides by applying thermodynamic analyses based on a first principles computation database. We reveal the stability trends among different chemistries and identify the effect of cations, anions, and Li/Na content on moisture stability. Our results identify promising materials systems to simultaneously achieve desirable moisture stability and electrochemical stability, and provide the design principles for the development of air-stable solid electrolytes.     

Critical challenges and progress of solid garnet electrolytes for all-solid-state batteries

Significant safety problems and poor cyclic stability of conventional lithium-ion batteries, which based on organic liquid electrolytes, hinder their practical application, while all-solid-state batteries (ASSBs) are considered the most promising candidates to replace traditional lithium-ion batteries. As a critical component of ASSBs, solid-state electrolytes play an essential role in ion transport properties and stability. At present, the solid garnet electrolyte is considered as one of the most promising electrolytes because of its excellent performance. However, it still faces many challenges in ionic conductivity, air stability, electrode/electrolyte interface, and lithium dendrites. Therefore, this review is concerned about the up-to-date progress and challenges which will greatly influence the large-scale application of solid garnet electrolytes. Firstly, various ways to improve the ionic conductivity of solid garnet electrolytes are comprehensively summarized. Then, the stability of solid garnet electrolytes in the air is carefully discussed. Secondly, the latest progress in interface engineering between anode/cathode and solid garnet electrolytes treated by different methods is reported. The formation mechanism and influencing factors of lithium dendrites in the solid garnet electrolyte are systematically focused on. Finally, the development and innovation of composite solid garnet electrolytes and 3D garnet electrolytes are summarized in detail. Some important characterization techniques for studying the aforementioned problems are also summarized. Based on the current development of solid garnet electrolytes and solid-state batteries, further challenges and perspectives are presented.     

PEO-LITFSI-SiO2-SN System Promotes the Application of Polymer Electrolytes in All-Solid-State Lithium-ion Batteries

All-solid-state polymer lithium-ion batteries are ideal choice for the next generation of rechargeable lithium-ion batteries due to their high energy, safety and flexibility. Among all polymer electrolytes, PEO-based polymer electrolytes have attracted extensive attention because they can dissolve various lithium salts. However, the ionic conductivity of pure PEO-based polymer electrolytes is limited due to high crystallinity and poor segment motion. An inorganic filler SiO₂ nanospheres and a plasticizer Succinonitrile (SN) are introduced into the PEO matrix to improve the crystallization of PEO, promote the formation of amorphous region, and thus improve the movement of PEO chain segment. Herein, a PEO₁₈−LiTFSI−5 %SiO₂−5 %SN composite solid polymer electrolyte (CSPE) was prepared by solution-casting. The high ionic conductivity of the electrolyte was demonstrated at 60 °C up to 3.3×10⁻⁴ S cm⁻¹. Meanwhile, the electrochemical performance of LiFePO₄/CSPE/Li all-solid-state battery was tested, with discharge capacity of 157.5 mAh g⁻¹ at 0.5 C, and capacity retention rate of 99 % after 100 cycles at 60 °C. This system provides a feasible strategy for the development of efficient all-solid-state lithium-ion batteries.     

可拉伸聚合物基复合固体电解质研究进展

未来可穿戴电子器件和系统需要柔性电池提供致密、 安全且可靠的电能源保障. 发展兼具可拉伸性和高离子电导率的固体电解质技术是实现全固态锂电池柔性化, 进而满足上述要求的关键之一. 本文综合评述了提升聚合物基复合固体电解质离子传导性能的主要机制和研究进展, 分析了在不同尺度下解耦离子传导和力学承载功能, 进而在弯折、 拉伸等形变工况下维持离子传导性能稳定的策略, 介绍了有助于推动可拉伸聚合物基复合固体电解质研究的几类先进表征技术, 并展望了未来研究工作的重点方向.     

卤化物固态电解质研究进展

全固态电池因其高能量密度和高安全性而成为具有发展前景的下一代储能技术。开发具有高室温离子电导率、优异化学/电化学稳定性、良好正/负极兼容性的固态电解质是实现全固态电池实用化的关键。卤化物固态电解质因其优异的电化学窗口、高正极稳定性、可接受的室温锂离子电导率等优势,受到了广泛的关注。本文通过对近年来卤化物电解质的相关研究进行总结,综述了该类电解质的组成、结构、离子传导路径及制备方法,并分析了金属卤化物电解质的电导率、稳定性特点,归纳了近年来该电解质在全固态电池中具有代表性的应用,并基于以上总结和分析,指出了卤化物固态电解质的研究难点及发展方向。     

Ionic liquids to the rescue? Overcoming the ionic conductivity limitations of polymer electrolytes

Polymer electrolytes – solid polymeric membranes with dissolved salts – are being intensively studied for use in all-solid-state lithium-metal-polymer (LMP) batteries to power consumer electronic devices. The low ionic conductivity at room temperature of existing polymer electrolytes, however, has seriously hindered the development of such batteries for many applications. The incorporation of salts molten at room temperature (room temperature ionic liquids or RTILs) into polymer electrolytes may be the necessary solution to overcoming the inherent ionic conductivity limitations of ‘dry’ polymer electrolytes.     

锂硫银锗矿固态电解质研究进展

全固态电池因其较高的安全性和能量密度而成为下一代电动汽车和智能电网用储能器件的重点研究方向之一。开发具有高室温锂离子电导率、化学/电化学稳定性优异、对电极材料兼容性优异等特点的固态电解质材料是推动全固态电池发展的重要研究课题之一。硫化物电解质因其相对较高的室温电导率(~10⁻³ S∙cm⁻¹)、较低的电解质/电极固-固界面阻抗等优点而在众多无机固体电解质材料中成为研究热点。本文基于作者多年研究成果和当前国内外发表的相关工作,从电解质的结构、离子传导、合成、综合性能改善及在全固态电池中的应用等方面系统总结了锂硫银锗矿固态电解质材料研究,并分析了该类电解质面临的问题和挑战,最后探讨了其未来可能的研究方向和发展趋势。     

A Gel Polymer Electrolyte with 2D Filler-reinforced for Dendrite Suppression Li-Ion Batteries

Gel polymer electrolytes (GPEs) incorporate both the high ionic conductivity of organic liquid electrolyte and the high safety performance of all-solid-state electrolytes (ASSEs), greatly improving the electrochemical performance of solid polymer electrolytes (SPEs). However, the practical application of GPEs is still limited by inferior interface compatibility, lithium dendrites, etc. Herein, we prepared GPEs based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) further co-blended the two-dimensional sheet inorganic filler hectorite and poly(methyl methacrylate) (PMMA) to improve the mechanical and electrochemical properties of the GPEs. When the content of PMMA and hectorite is optimal, this GPEs have an ionic conductivity of 1.06×10⁻³ S cm⁻¹ and outstanding lithium symmetric cells cycle time of more than 3000 h, indicating that the introduction of filler effectively inhibits the growth of lithium dendrites at room temperature. Moreover, the GPEs adopt a relatively simple solution casting method to provide a fresh idea for the synthesis of high-performance GPEs.     

Improving the performance of all-solid-state supercapacitors by modifying ionic liquid gel electrolytes with graphene nanosheets prepared by arc-discharge

Ionic liquid gel polymers have widely been used as the electrolytes in all-solid-state supercapacitors, but they suffer from low ionic conductivity and poor electrochemical performance. Arc discharge is a fast, low-cost and scalable method to prepare multi-layered graphene nanosheets, and as-made graphene nanosheets （denoted as ad-GNSs） with few defects, high electrical conductivity and high thermal stability should be favorable conductive additive materials. Here, a novel ionic liquid gel polymer electrolyte based on an ionic liquid （EM1MNTF2） and an copolymer （P（VDF-HFP）） was modified by the addition of ad-GNSs as an ionic conducting promoter. This modified gel electrolyte shows excellent thermal stability up to 400 ℃ and a wide electrochemical window of 3 V. An all-solid-state supercapacitor based on commercial activated carbon was fabricated using this modified ionic liquid gel polymer electrolyte, which shows obviously improved electrochemical behaviors compared with those of the corresponding all-solid-state supercapacitor using pure ionic liquid gel polymer electrolyte. Specially, smaller internal resistance, higher specific capacitance, better rate performance and cycling stability are achieved. These results indicate that the ionic liquid gel polymers modified by ad-GNSs would be promising and suitable gel electrolytes for high performance all-solid-state electrochemical devices.     

稀土溴化物固态电解质材料在全固态电池中的应用研究进展北大核心CSCD

全固态锂电池具有优异的安全性能和能量密度,有望成为替代传统有机液态锂离子电池的下一代储能产品。固态电解质是决定全固态电池性能的关键材料,其中卤化物固态电解质,尤其是稀土溴化物固态电解质(RE-BSEs)材料近年来在离子电导率(高达mS/cm数量级)和电化学稳定性(1.5~3.4 V vs.Li^(+)/Li)等方面取得了一系列重要的研究进展,具有可期待的应用前景。本文通过对RE-BSEs的发展历程、研究进展、技术瓶颈、发展方向和应用前景等方面进行综述和回顾,给予研究人员在RE-BSEs的合成方法、锂离子传输机理、构效关系和材料设计等方面的参考和启发。稀土是我国乃至世界的重要战略资源,RE-BSEs材料的研究和重要成果明示了稀土元素在固态离子导体和新能源领域的重大价值,因此,做好稀土在该方面的研究工作对能源结构调整、节能减排、碳达峰和碳中和具有重大意义。     

基于聚碳酸丙烯酯基聚合物电解质和有机正极的全固态钠电池

Sodium-ion batteries (SIBs) are promising candidates to replace lithium-ion batteries (LIBs) to meet the emergent requirements of various commercial applications. SIBs and LIBs are similar in many aspects, including their reduction potentials, approximate energy densities, and ionic semidiameters. Analogously, safety issues, including liquid leakage, high flammability, and explosiveness limit the usage of SIBs. All-solid-state batteries have the potential to solve the aforementioned problems. However, polycarbonates as promising solid electrolytes have been rarely exploited in all-solid-state SIBs. In addition, organic electrode materials, including non-conjugated redox polymers, carbonyl compounds, organosulfur compounds, and layered compounds, have been intensively investigated as part of various energy storage systems owing to their low cost, environmental friendliness, high energy density, and structural diversity. Nevertheless, the dissolution of small organic compounds in organic-liquid electrolytes has hindered its further applications. Fortunately, the utilization of solid polymer electrolytes combined with organic electrode materials is a promising method to prevent dissolution into the electrolyte and improve the cycling performance of SIBs. Thus, we proposed the utilization of a poly(propylene carbonate) (PPC)-based solid polymer electrolyte and cellulose nonwoven with a 3, 4, 9, 10-perylene-tetracarboxylicacid-dianhydride (PTCDA) cathode in an all-solid-state sodium battery (ASSS). The solid electrolyte significantly enhanced the safety of the SIB and was successfully synthesized via a facile method. The morphology of the as-prepared solid electrolyte was examined by electron scanning microscopy (SEM). Furthermore, the electrochemical performances of the PTCDA/Na battery with organic-liquid and solid electrolytes at room temperature were compared. The SEM results demonstrated that the solid polymer electrolyte and sodium bis(fluorosulfonyl)imide (NaFSI) were evenly distributed inside the pores of the nonwoven cellulose. The ionic conductivity of the composite solid polymer electrolyte (CSPE) at room temperature was 3.01 × 10^-5 S·cm^-1, suggesting that the CSPE was a promising candidate for commercial applications. In addition, the ASSS showed significantly improved cycling performance at a current density of 50 mAh·g^-1 with a high capacity retention of 99.1%, whereas the discharge capacity of the liquid PTCDA/Na battery was only 24.6mAh·g^-1 after 50 cycles. This indicated that the cycling performance of the PTCDA cathode in the SIB was largely improved by preventing the dissolution of the PTCDA cathode material in the electrolyte. Electrochemical impedance spectroscopy results demonstrated that the CSPE was compatible with the organic cathode electrode.     

五种1-烷基-2,3-二甲基咪唑型离子液体的合成及作为Li/LiFeO_4电池电解液的研究

合成了五种新的1-烷基-2,3-二甲基咪唑二(三氟甲基磺酰)亚胺离子液体(alkyl-DMimTFSI).以离子液体作为Li/LiFeO4电池电解液,分别考察不同烷基(正丁基、正戊基、正辛基、异辛基和正癸基)对电解液理化性质、界面性质和电池行为的影响.结果表明离子液体的电化学窗口都可以达到5.6V(-0.4～5.2Vvs.Li+/Li),显示它们具有较好的电化学稳定性.加入碳酸亚乙烯酯作为添加剂后,离子液体电解液在Li负极形成稳定的固体电解质相界面膜(SEI),从而提高了Li负极的稳定性,保护了Li片不受腐蚀.电化学阻抗和循环伏安分析进一步揭示LiFeO4正极与离子液体电解液也有良好的兼容性.此外,研究还表明离子液体中烷基种类严重影响它们的电池行为.采用butyl-DMimTFSI和amyl-DMimTFSI电解液体系的电池充放电容量和可逆性明显优于另外三种离子液体,它们的首次放电容量分别达到145和152.6mAh/g,并表现出良好的充放电循环性能.因粘度最大,采用isooctyl-DMimTFSI电解液的电池首次放电容量仅为8.3mAh/g,但添加碳酸丙烯酯(质量比1∶1)稀释后首次放电容量上升至132.4mAh/g.     

锂无机固体电解质*

全固态锂离子二次电池具有更大能量密度和更高的安全使用性能,在未来的电动汽车和蓄能电站上有很好的应用前景。本文对一些典型的锂无机固体电解质进行分类讨论,对它们的性能、结构和导电机理进行评述。这些固体电解质具有较高的离子导电率,是目前的研究热点。文章总结了影响其导电率的几个重要因素以及作为理想锂无机固体电解质的几个基本要求。     

Liquid-Free All-Solid-State Zinc Batteries and Encapsulation-Free Flexible Batteries Enabled by In Situ Constructed Polymer Electrolyte

Zn batteries are usually considered as safe aqueous systems that are promising for flexible batteries. On the other hand, any liquids, including water, being encapsulated in a deformable battery may result in problems. Developing completely liquid-free all-solid-state Zn batteries needs high-quality solid-state electrolytes (SSEs). Herein, we demonstrate in situ polymerized amorphous solid poly(1,3-dioxolane) electrolytes, which show high Zn ion conductivity of 19.6 mS cm⁻¹ at room temperature, low interfacial impedance, highly reversible Zn plating/stripping over 1800 h cycles, uniform and dendrite-free Zn deposition, and non-dry properties. The in-plane interdigital-structure device with the electrolyte completely exposed to the open atmosphere can be operated stably for over 30 days almost without weight loss or electrochemical performance decay. Furthermore, the sandwich-structure device can normally operate over 40 min under exposure to fire. Meanwhile, the interfacial impedance and the capacity using in situ-formed solid polymer electrolytes (SPEs) remain almost unchanged after various bending tests, a key criterion for flexible/wearable devices. Our study demonstrates an approach for SSEs that fulfill the requirement of no liquid and mechanical robustness for practical solid-state Zn batteries.     

全固态电池界面的研究进展

Owing to the serious energy crisis and environmental problems caused by fossil energy consumption, development of high-energy-density batteries is becoming increasingly significant to satisfy the rapidly growing social demands. Lithium-ion batteries have received widespread attention because of their high energy densities and environmental friendliness. At present, they are widely used in portable electronic devices and electric vehicles. However, security aspects need to be addressed urgently. Substantial advances in liquid electrolyte-based lithium-ion batteries have become a performance bottleneck in the recent years. Traditional lithium-ion batteries use organic liquids as electrolytes, but the flammability and corrosion of these electrolytes considerably limit their development. Continuous growth of lithium dendrites can pierce the separator, leading to electrolyte leakage and combustion, which is a serious safety hazard. Replacement of organic electrolytes with solid-state electrolytes is one of the promising solutions for the development of next-generation energy storage devices, because they have high energy densities and are safe. Solid electrolytes can remarkably alleviate the safety hazards involved in the use of traditional liquid-based lithium-ion batteries. In addition, the composite of solid-state electrolytes and lithium metal is expected to result in a higher energy density. However, due to the lack of fluidity of the solid electrolytes, problems such as limited solid-solid contact area and increased impedance at the interface when solid-state electrolytes are in contact with electrodes must be solved. The localized and buried interface is a major drawback that restricts the electrochemical performance and practical applications of the solid-state batteries. Fabrication of a stable interface between the electrodes and solid-state electrolyte is the main challenge in the development of solid-state lithium metal batteries. All these aspects are critical to the electrochemical performance and safety of the solid-state batteries. Current research mainly focuses on addressing the problems related to the solid-solid interface in solid-state batteries and improving the electrochemical performance of such batteries. In this review, we comprehensively summarize the challenges in the fabrication of solid-state batteries, including poor chemical and electrochemical compatibilities and mechanical instability. Research progress on the improvement strategies for interface problems and the advanced characterization methods for the interface problems are discussed in detail. Meanwhile, we also propose a prospect for the future development of solid-state batteries to guide the rational designing of next-generation high-energy solid-state batteries. There are many critical problems in solid-state batteries that must be fully understood. With further research, all-solid-state batteries are expected to replace the traditional liquid-based lithium-ion batteries and become an important system for a safe and reliable energy storage.