锂离子电池高压电解液

锂离子电池作为一种绿色可充电电池,具有较高能量密度以及功率密度,是便携式电子产品的首选,并逐渐应用于动力汽车领域。为了更好地满足其应用需求,需要进一步提高当前锂离子电池的能量密度。不同于高压正极材料的快速发展,传统电解液在较高工作电压下容易分解,很大程度上阻碍了高能量密度锂离子电池的商业化应用。作为锂离子电池的重要组分,电解液对其多方面性能均具有重要影响,因此亟需提高电解液的工作电压以解决锂离子电池能量密度较低的问题。本文从新型有机溶剂以及高电压添加剂两方面入手,综述近年来国内外高压电解液的研究进展,介绍理论计算对于设计高压电解液的作用,并对高压电解液的发展及前景做出总结和展望。     

量子化学方法在锂离子电池电解液研究中的应用

总结了近年来量子化学方法在锂离子电池电解液研究中的应用进展,阐述了量子化学方法在新型锂盐设计、功能添加剂作用机理分析和电极/电解液界面膜的形成过程研究中发挥的作用,对其用来设计锂离子电池电解液功能分子作出展望。     

锂离子电池高电压和耐燃电解液研究进展

电解液作为锂离子电池的重要组成部分,起着传输离子的作用,电解液的性质对电池的容量、循环性能及安全性能等影响巨大.近年来,随着高电压、高能量密度锂离子电池的开发应用,现有常规碳酸酯电解液存在正极稳定性差、闪点低、易燃烧等问题.因此,发展高电压耐燃电解液是应用高电压高容量正极材料、发展高电压高容量高安全性锂离子电池的迫切需要.主要综述了高电压电解液、耐燃性电解液及兼具抗氧化性和耐燃性的高浓度电解液的研究进展和现状.在此基础上,对锂离子电池新型电解液的发展方向进行了展望.     

高比能锂离子电池高电压电解液的设计

自便携式电子设备以及电动汽车问世后,锂离子电池储能设备已经难以满足当前的生活与生产需求.锂离子电池作为商业储能设备市场的主要占有者,正朝着更高的能量密度、更长久的使用寿命以及更高的安全性能等方向发展.虽然通过提高锂离子电池的截止电压可以达到提升电池重量密度和体积密度的效果,但电池体系在高电压下将非常不稳定,这将导致锂离子电池的循环性能迅速衰减.同时,大量的电解液分解产物的堆积,导致电池的界面阻抗上升.另一方面,气体的生成形成了电池的安全隐患.本文针对高电压电解液的溶剂设计和电解液添加剂设计两个方面,回顾了过去一段时间里高电压电解液的发展.根据当前的理论研究基础,提出了高比能锂离子电池电解液的设计重心和未来该领域的主要研究方向.     

锂离子电池高电压电解液

开发高电压正极材料是发展高能量密度锂离子电池的重要途径之一。常规电解液在高电压下容易与正极材料表面发生副反应,影响高电压正极材料性能的发挥,因此,高电压电解液引起了人们广泛的关注。本文主要从新型溶剂体系和常规碳酸酯溶剂体系两方面对锂离子电池高电压电解液进行综述与评价,提出了现有电解液的不足及面临的问题。从电解液溶剂分子设计理论入手,分析了砜类溶剂、腈基溶剂和离子液体等新型溶剂作为高压电解液溶剂的优缺点,同时探讨了不同种类添加剂在常规碳酸酯溶剂体系中的作用机理。此外,本文还介绍了理论计算方法在锂离子电池高电压电解液研究中的应用,并对其在设计新型高电压电解液中的应用前景进行了展望。     

锂离子电池电解液的研究进展(英文)

综述现今锂离子电池电解液的研究进展 .评估了电解液中锂盐、溶剂、填加剂以及杂质等对电解液的电导、固体电解质相界面 (SEI)的形成、电池循环寿命等的影响     

LiBOB-PC/DEC电解液性质研究

合成锂离子电池新型电解质锂盐L iBOB,并与PC/DEC溶剂配成电解液.室温下研究了L iBOB-PC/DEC电解液电导率随锂盐浓度的变化规律及其用于L i/ARG电池充放电循环性能的最佳组成配比,为0.5mol.L-1L iBOB-PC/DEC(3∶7).应用交流阻抗和循环伏安法研究了该最佳电解液的电化学性质及其电极/界面状态,结果显示,石墨电极在这种电解液中可形成良好的SEI膜.     

锂离子电池低温性能改善研究进展

锂离子电池因其能量密度高,循环寿命长等优点已成为新型动力电池领域的研究热点,但其温度特性尤其是低温性能较差制约着锂离子电池的进一步使用. 本文综述了锂离子电池低温性能的研究进展,系统地分析了锂离子电池低温性能的主要限制因素. 从正极、电解液、负极三个方面讨论了近年来研究者们提高电池低温性能的改性方法. 并对提高锂离子电池低温性能的发展方向进行了展望.     

新型添加剂全氟辛酸铵对提高锂离子电池安全性能的研究

报导可显著提高锂离子电池安全性的新型电解液添加剂全氟辛酸铵(APC). UL 94 可燃性试验显示添加0.70 wt% APC能使有机电解液的火焰传播速率下降33%. 差示扫描量热法(DSC)测试表明APC显著减弱了嵌锂碳电极和电解液之间的放热反应, 并将其热不稳定温度由138.0 ℃提高到167.5 ℃. 交流阻抗检测显示APC的加入明显降低了碳材料电极的界面阻抗, 并且提高了在储存过程中其固态电解质界面(SEI)层的稳定性. 添加APC还能有效地提高Li/MCMB电池充放电循环性能和库仑效率.     

锂离子电池正极界面修饰用电解液添加剂

提高电压是提高锂离子电池比能量的重要途径之一。例如,LiNi_0.5Mn_1.5O₄(4.7 V)、LiNiPO₄(5.1 V)和富锂锰基等电极材料在较高的充电截止电压下表现出较高的能量密度和较低的成本,具有很好的应用前景。另外,提高LiCoO₂和三元电池体系的充电截止电压是提升电池能量密度的简单有效措施。但是,当电池充电截止电压提高时,不仅会造成电解液在正极/电解液界面的氧化分解,还会加速正极中金属阳离子在电解液中的溶解,造成电池循环性能和安全性下降。采用不同的正极界面修饰用电解液添加剂,既可以有效钝化正极/电解液界面,抑制电解液的分解,还可以有效抑制正极结构的破坏。本文从添加剂的分子结构出发,介绍了磺酸酯、硼酸酯、磷酸酯、氟代碳酸酯、腈类、酸酐和锂盐等添加剂在正极界面的相关研究成果,并对不同添加剂的作用机理进行了详细的解释和归纳;另外,介绍了添加剂的联用技术在不同电池体系中的最新研究成果;最后,对新型正极界面修饰用电解液添加剂的开发进行了展望。     

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.     

全固态锂金属电池表界面化学的研究进展

传统的锂金属电池存在电解液易泄漏、 易燃等安全隐患, 因此开发不燃性全固态电解质对于解决锂金属电池安全问题至关重要, 而如何有效降低固体电解质与电极之间的界面电阻是发展高性能全固态锂金属电池的关键. 针对如何优化全固态锂金属电池表界面的问题, 本文综述了全固态锂金属电池电极和电解质表面修饰的最新研究进展, 对提高界面接触和降低界面电阻的传统方法进行了探讨, 分析并点评了新型的表面修饰技术, 为进一步提高全固态锂金属电池的综合性能提供新思路. 最后, 对全固态锂金属电池的研究前景进行了展望.     

聚碳酸酯基固态聚合物电解质的研究进展

液态锂离子电池由于采用易泄露、易挥发、易燃烧的碳酸酯有机溶剂,在高温或极端条件下使用时,存在极大的安全隐患.使用固态电解质替代液态电解液,可以从根本上避免此类安全问题的发生,与此同时还可以大幅度提升固态锂电池的能量密度.固态电解质又分为无机固态电解质和聚合物固态电解质2大类.无机固态电解质能够在宽的温度范围内保持化学稳定性,并且电化学窗口较宽,机械强度更高,室温离子电导率较高,但脆性较大,柔韧性差,制备工艺复杂,成本较高.聚合物固态电解质,室温离子电导率偏低,难以满足室温锂离子电池的应用,但其加工成型容易,形状可变.比较而言,固态聚合物电解质,更适宜大规模生产,离产业化相对更近.固态聚合物电解质中研究较多的是聚醚基固态聚合物电解质(如聚环氧乙烷和聚环氧丙烷),但其缺点是室温离子电导率低,需要对其改性或进一步开发综合性能更加优异的其他固态聚合物电解质.聚碳酸酯基固态聚合物电解质由于其特殊的分子结构(含有强极性碳酸酯基团)以及高介电常数,可以有效减弱阴阳离子间的相互作用,提高载流子数量,从而提高离子电导率,因此被认为是一类非常有前途的固态聚合物电解质体系.基于此,本文重点综述了最近研究热点的聚碳酸酯基固态聚合物电解质,包括聚(三亚甲基碳酸酯)体系、聚(碳酸丙烯酯)体系、聚(碳酸乙烯酯)体系和聚(碳酸亚乙烯酯)体系等,并详细阐述了上述每种聚碳酸酯基固态聚合物电解质的制备、电化学性能、优缺点及改性手段,归纳出其离子配位-解配位过程和离子扩散机制,还对聚碳酸酯基固态聚合物电解质的未来发展方向和研究趋势望进行了预测和展望.     

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。     

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。     

Toward Practical All-solid-state Batteries with Sulfide Electrolyte: A Review

Sulfide-based solid-state electrolytes with ultrahigh lithium ion conductivities have been considered as the most promising electrolyte system to enable practical all-solid-state batteries. However, the practical applications of the sulfide-based all-solid-state batteries are hindered by severe interfacial issues as well as large-scale material preparation and battery fabrication problems. Liquid-involved interfacial treatments and preparation processes compatible with current battery manufacturing capable of improving electrode/electrolyte interface contacts and realizing the mass production of sulfide electrolytes and the scalable fabrication of sulfide-based battery component have attracted considerable attention. In this perspective, the current advances in liquid-involved treatments and processes in sulfide-based all-solid-state batteries are summarized. Then relative chemical mechanisms and existing challenges are included. Finally, future guidance is also proposed for sulfide-based batteries. Focusing on the sulfide-based all-solid-state batteries, we aim at providing a fresh insight on understandings towards liquid-involved processes and promoting the development of all-solid-state batteries with higher energy density and better safety.     

Power sources for portable electronics and hybrid cars: lithium batteries and fuel cells

The activities in progress in our laboratory for the development of batteries and fuel cells for portable electronics and hybrid car applications are reviewed and discussed. In the case of lithium batteries, the research has been mainly focused on the characterization of new electrode and electrolyte materials. Results related to disordered carbon anodes and improved, solvent-free, as well as gel-type, polymer electrolytes are particularly stressed. It is shown that the use of proper gel electrolytes, in combination with suitable electrode couples, allows the development of new types of safe, reliable, and low-cost lithium ion batteries which appear to be very promising power sources for hybrid vehicles. Some of the technologies proven to be successful in the lithium battery area are readapted for use in fuel cells. In particular, this approach has been followed for the preparation of low-cost and stable protonic membranes to be proposed as an alternative to the expensive, perfluorosulfonic membranes presently used in polymer electrolyte membrane fuel cells (PEMFCs).     

An Artificial Lithium Protective Layer that Enables the Use of Acetonitrile‐Based Electrolytes in Lithium Metal Batteries

The resurgence of the lithium metal battery requires innovations in technology, including the use of non‐conventional liquid electrolytes. The inherent electrochemical potential of lithium metal (?3.04 V vs. SHE) inevitably limits its use in many solvents, such as acetonitrile, which could provide electrolytes with increased conductivity. The aim of this work is to produce an artificial passivation layer at the lithium metal/electrolyte interface that is electrochemically stable in acetonitrile‐based electrolytes. To produce such a stable interface, the lithium metal was immersed in fluoroethylene carbonate (FEC) to generate a passivation layer via the spontaneous decomposition of the solvent. With this passivation layer, the chemical stability of lithium metal is shown for the first time in 1 m LiPF₆ in acetonitrile.     

氟代溶剂在锂金属电池中的应用

近年来，锂金属电池由于具有较高的能量密度而成为储能领域的研究热点。电解液作为锂金属电池的“血液”发挥着至关重要的作用。在传统锂离子电池电解液中，锂金属负极与电解液之间的界面副反应严重并伴随着锂枝晶生长，从而导致安全隐患以及循环寿命缩短等问题。在解决锂金属负极问题上，电解液调控策略具有易操作性和有效性，因而在推动锂金属电池发展方面具有举足轻重的地位。氟代电解液是目前重要的研究方向，氟代电解液在循环过程中能够在电极表面形成富含LiF的固体电解质界面膜(SEI)；该界面膜不仅可以有效抑制负极锂枝晶的形成，并且在正极方面能够大幅提高电解液的氧化稳定性，从而提升高电压正极的适配性和锂金属电池的循环稳定性。氟代电解液中氟代溶剂/氟代锂盐的分子结构对电解液的溶剂化结构有重要影响。当氟代溶剂分子中氟原子的位置与数量不同时，氟代溶剂的物理化学性质也会随之发生变化，进而改变了电解液与电极的界面反应性。因此，氟代溶剂能够起到调制SEI膜成分和结构的作用，是决定电池性能的关键因素。本文总结了应用于锂金属电池的主要氟代溶剂，尤其是近几年来发展的新型氟代溶剂；着重介绍了高度氟代的溶剂分子作为局域超浓电解液的稀释剂，以及对溶剂进行精准分子设计得到的部分氟代溶剂等。此外，本文还分析探讨了氟代溶剂分子与电池性能之间的构效关系，展望了构建新型氟代溶剂分子的策略，希望能对电解液溶剂分子的结构设计以及构效关系的评估有一定的启发意义。     

氟代溶剂在锂金属电池中的应用

Lithium metal batteries, which use lithium metal as the anode, have attracted tremendous research interest in recent years, owing to their high energy density and potential for future energy storage applications. Despite their advantages such as high energy density, the safety concerns and short lifespan significantly impede their practical applications in transportation and electronic devices. Tremendous efforts have been devoted to overcoming these problems, including materials design, interface modification, and electrolyte engineering. Among these strategies, electrolyte regulation plays a key role in improving the efficiency, stability, and safety of lithium metal anodes. As an important class of electrolyte components, fluorinated solvents, which can decompose to form LiF-rich interphase layers on both anode and cathode, have been proven to enhance the stability of lithium metal anodes and improve the oxidative stability of the electrolytes. Meanwhile, the spatial structure of fluorinated solvents, such as the number and sites of fluorine atoms, can influence the physicochemical properties of the electrolytes and the compositions/structure of the solid-electrolyte interphase, which eventually dictates the cycling performance of Li metal batteries. Recently, many fluorinated solvents with different molecular structures have been designed to regulate the solvation structure of electrolytes, and these solvents exhibit novel electrochemical properties in lithium metal batteries. However, there are few comprehensive reviews that summarize the fluorinated solvents used in Li metal batteries and discuss their functions in electrolytes and their physicochemical properties. This review summarizes the novel fluorinated solvents used in lithium metal batteries in recent years, which have been classified into three parts: diluents, traditional solvents, and novel molecules, based on their functions in the electrolytes. In every part, the understanding of the interactions between fluorinated solvents and Li ions, the decomposition mechanism of fluorinated solvents at the interface of the electrode, the functions of fluorinated solvents in the electrolytes, and the structure-activity relationship between the fluorinated solvents and battery performance have been comprehensively summarized and discussed. Moreover, the advantages and disadvantages of fluorinated solvents have been discussed, and the importance of precisely controlling the number of fluorine atoms and the structure of fluorinated solvents has been emphasized. At the end of this review, a perspective for designing new fluorinated solvents has been proposed. We believe that this review can provide insights on designing novel fluorinated solvents for high-performance Li metal batteries.