锂离子电池硅-碳负极材料的研究进展

硅因具有大的比容量,极有希望成为下一代锂离子电池的主要负极材料。硅基负极材料工业化需其具备较高的比容量、良好的循环性能并能够进行工业生产。综述了硅-碳复合材料的研究进展,介绍了各类硅-碳复合物的制备方法、结构和电化学性能,提出制备低成本、性能稳定的硅-碳复合物将成为硅基材料研究的主导方向。     

硅材料在锂离子电池中的应用研究进展

硅材料作为锂离子电池负极材料具有比容量大的优点,是高容量锂离子负极材料的研究热点之一.综述了近年来锂离子电池硅负极材料的研究进展.分别对硅及含硅材料作为锂离子电池负极材料的发展过程、充放电特性、储锂机理及影响其储锂的各因素进行了分析和总结,并对其存在的问题进行了分析.探讨了采用不同复合物、不同制备方法和合成硅化物等改性方法来提高其循环性能的可行性.指出纳米硅基复合物将是硅负极材料最有希望的发展方向.     

锂离子电池硅-碳负极材料的研究进展

硅基负极材料因具有较高的理论储锂容量,将替代传统的石墨负极材料成为下一代锂离子电池最有前景的负极材料之一。然而,硅作为负极材料体积膨胀率(可达到300%)大、导电率低、易被电解液分解产生的HF腐蚀,这些缺点限制了其在商业应用中的发展。碳具有稳定性高、导电性好、价格低、来源广等优点,但其理论储锂容量较低,仅约为硅的1/10。为解决锂离子电池硅材料存在的问题,目前主要采用将硅与碳进行复合的办法,制备出储电量高、导电性好、循环性能优异的硅-碳复合负极材料。重点从硅碳复合结构和制备方法两个方面阐述了硅-碳复合负极材料的研究进展,认为"鸡蛋"结构能够有效地提高循环性能和安全性能,但是目前仍然不能够规模化生产。最后提出研究发展思路,应用胶体颗粒共凝胶法设计制备了一种特殊的硅-碳复合核壳结构。     

锂电池的研究进展

综述了近年来在锂电池正极材料、负极材料和电解质材料且装方面的研究进展，并对锂电池的发展作了展望。     

锂离子电池负极材料的制备及应用进展

锂离子电池作为最具开发应用前景的新型储能材料,不仅具有安全、高效、对环境无污染的优点,而且具备相对质量轻、工作电压高、能量密度大、循环寿命长等一系列优势,已成为新型能源领域的研究热点。综述了锂离子电池负极材料中碳基负极材料、硅基负极材料、锡基负极材料和金属锂负极材料的合成、性质,以及在材料的结构设计、制备工艺等方面的研究进展。     

锂离子电池硅基负极材料研究进展

锂离子电池硅基负极材料由于具有高的理论比容量,低的脱嵌锂电位,与电解液反应活性低等优点而成为研究热点。本文综述了近年来硅基材料作为锂离子负极材料的研究进展,包括纳米硅、硅基薄膜、硅-金属复合材料、硅-碳材料,分析硅基材料作为锂离子电池负极材料的研究前景和发展方向。     

硅负极材料的储锂机理与电化学改性进展

硅作为锂离子电池负极材料具有极高的比容量,被认为是最有应用潜力的下一代锂离子电池负极候选材料。本文系统总结了硅负极材料的电化学储锂特性和储锂机理,分析了硅负极材料存在的主要问题及原因。针对存在的问题,从嵌脱锂过程硅材料粉化调控、稳定固体电解质界面膜(SEI膜)的构建和硅材料导电性调变3方面对硅负极材料的电化学改性进展进行了评述,并指出了硅负极储锂材料今后的研究方向。     

锂离子电池Sn基负极材料研究进展

综述了锂电池用Sn基负极材料近年来的发展现状,着重讨论了Sn基氧化物、Sn基复合氧化物、Sn基合金以及Sn基复合物等Sn基负极材料的制备方法、性能特点、存在问题以及改善途径。指出单一方法难以全面改善Sn基负极材料的性能,综合运用结构优化、成分控制、掺入基质以及优化还原剂、黏合剂和电解质添加剂等途径才能更好地改善Sn基负极材料的电化学性能。最后,对Sn基负极材料的研究趋势进行了展望,并指出以石墨烯为基质的Sn基复合材料是今后研究的重要方向。     

非晶LiSiON薄膜电解质的全固态薄膜锂电池性能

全固态薄膜锂电池(TFLB)是理想的微电子系统电源.目前报道的固态非晶电解质存在离子电导率偏低的问题,限制了TFLB性能的提升.本工作采用磁控溅射法制备了一种新型非晶锂硅氧氮(LiSiON)薄膜用作TFLB的固态电解质.结果表明,优化制备条件后的LiSiON薄膜具有6.3×10–6 S·cm–1的高离子电导率以及超过5...     

全固态锂电池中金属锂负极及其界面设计的研究进展

锂金属具有低的氧化还原电位(-3.04 V vs标准氢电极)和高比容量(3860 mAh/g),是理想的锂二次电池负极材料.由金属锂负极/固态电解质/嵌锂正极组装的固态锂电池,有望成为未来航空航天、机器人、高端电子和电动汽车等相关技术产业的动力源.然而,在充放电过程中,由于锂的不均匀沉积-溶解造成锂与电解质接触面产生大量树枝状枝晶,并沿着电解质方向不断生长,最终造成电池内部短路而失效.使用较高杨氏模量的固态电解质,可以很大程度上阻挡锂枝晶的生长,但仍不能满足电池长循环和安全性的要求.此外,金属锂与固态电解质表面是固固接触,造成了界面电阻大以及金属锂与固态电解质的界面反应等问题,这严重阻碍了固态锂金属电池的发展与使用.本文综述了近年来基于固态电解质的金属锂电池抑制锂枝晶生长和提高固固界面相容性的相关策略,并对金属锂/固态电解质界面设计的发展趋势进行展望.     

Molten salts for rechargeable batteries

The growing demand of advanced electrochemical energy storage devices for various applications, including portable electronic products, electric vehicles, and large-scale energy storage grids, has triggered extensive research interests and efforts on various rechargeable batteries such as lithium/sodium-ion batteries (LIBs/NIBs), aluminium-ion batteries (AIBs), liquid metal batteries (LMBs), and molten-air batteries (MABs) in the past decades. A key issue to push forward the development of these batteries is the exploration of high-performance electrodes and electrolytes, which calls for efficient and versatile synthetic methods. Molten salts (MSs), liquid-phase ionic compounds or mixtures, provide an effective platform to widen the reaction temperatures and enrich the chemical environments for the synthesis of novel electrode materials and electrolytes. In this review, the general principles of molten salts and recent research progresses on molten salt-based battery materials are surveyed. Molten-salt synthesis of electrode materials, including sintering and electrolysis, are emerging as competitive substitutes for conventional synthesis techniques. These methods have shown their effectiveness and uniqueness in adjusting the crystal structure, morphology, and performance of electrode materials for LIBs/NIBs, as suggested by recent progresses and applications of diverse cathodes (layered oxides, spinel oxides, polyanions, etc.) and anodes (metal oxides, alloys, carbons, etc.). Furthermore, the applications of molten salts as effective electrolytes are demonstrated in representative new-type secondary batteries including AIBs, LMBs and MABs. Finally, the emerging opportunities, challenges, and interesting research trends are envisioned to promote the further development of molten-salt methodology for rechargeable batteries.     

固态离子学的新应用

固态离子学是研究固体中快离子输运规律及其应用的科学。它是上世纪70年代发展起来的一门新兴学科, 重点研究具有快离子传导特性的固体电解质材料以及具有离子/电子混合传导特性的电极材料。近年来, 固体离子及混合导电化合物在二次电池、燃料电池、传感器、超级电容器、电色器件、太阳能电池等方面的应用取得了突破性进展, 锂离子电池在各种电子器件中的大规模应用及其新材料体系的发现[1-2]、钠硫电池在大规模储能应用中的领先地位、ZEBRA电池在储能市场上的崛起、固体氧传感器在市场上的稳步发展以及SOFC逐步迈进市场成为固态离子学领域一个个闪光点, 极大地促进了新能源利用、电动汽车开发以及智能电网建设等重大任务的实施, 多领域的科学家和工程技术人员投身到固态离子学的研究中。
　　在众多的新能源技术研究方向中, 高比能量二次电池的研究是当前热点, 也是目前电动汽车开发和智能电网建设公认的瓶颈技术。近几年, 金属电极电池技术的发展使人们对二次电池的未来充满了信心。以金属为负极的二次电池得益于金属电极本身极高的比容量。金属负极主要以碱金属锂、钠和碱土金属镁为代表, 其中锂的重量和体积比容量分别高达3860 mAh/g和2062 mAh/cm3, 远高于目前商业化的碳类负极材料, 成为未来高比能量二次电池的目标。近期, 以金属锂负极活性材料的锂硫电池和锂空气电池的研究在国内外如火如荼, 并不断取得进展。
　　这些电池不仅具有高比能量的特点, 更有价格低廉的绝对优势, 同时也存在尚需改进之处。(1)在锂硫电池方面, 美国Sion Power公司利用PolyPlus公司的锂负极保护膜技术, 有望实现锂硫电池能量密度500 Wh/kg及循环500次的目标[3]。就在近期, 英国Oxis Energy公司报道其研制的200 Wh/kg的锂硫电池预计循环1700~1800次后的容量维持率仍达80%, 该公司计划明年早些时候实现量产[4], 这无疑是对锂硫电池的有力推动。国内有众多研究锂硫电池的机构, 如防化研究院、国防科技大学、北京理工大学、上海硅酸盐研究所、南开大学等均研制了软包装锂硫电池[5]。上海硅酸盐研究所研制的硫电极在2C倍率下循环500次后比容量达到900 mAh/g以上。不过目前看来, 锂硫电池虽然前景良好, 但要在市场上展现其价值尚需开展很多工作。(2)在锂空气电池方面, 针对电解质隔膜、催化剂、载体等核心材料有大量的文献报道, 通过无碳电极设计以及基于LATP锂离子固体电解质的电池设计, 很好地改进了锂空气电池的基本性能[6-8], 但离实际应用还差距甚远, 其电池反应机理方面尚存在争议, 电池技术还没有取得公认的突破。然而, 以锂空气电池为代表的金属空气电池由于其极高的比能量仍是未来电动汽车无法抗拒的追逐目标。
　　金属负极电池的开发在很大程度上取决于固体电解质新体系和新型电极材料的开发, 固态离子学成为高比能量二次电池研究与开发必须掌握的一门重要的科学, 无论是已经获得规模化应用的LiCoO2和LiFePO4等锂离子电池正极材料, Na-β/β″-Al2O3、ZrO2等离子导体, 还是新近突破的Li10GeP2S12和Li7La3Zr2O12[1-2]等锂离子导体新体系, 都为实现锂金属电池新的突破以及锂电池的全固体化、从而从根本上解决锂离子电池的安全性问题奠定了坚实的基础。正因为如此, 锂离子电池的企业界也在大力拓展市场的同时, 不断关注新型二次电池以及固态离子学的进展, 仅以我国两年一届的全国固态离子学学术会议为例, 其规模也从1980年的数十人发展到2012年第16届全国会议的与会代表400余人, 其中近20%代表来自电池与材料企业。可以说, 未来固态离子学将越来越发挥其重要作用, 为新能源技术的发展保驾护航。     

锂离子电池用多孔电极结构设计及制备技术进展

随着人们对锂离子电池需求的日益增加, 高能量密度和高功率密度锂离子电池技术成为研究热点之一。材料改性及新材料开发能有效提高电池的能量密度, 除此以外, 孔隙率、孔径大小与分布、曲折度及电极组分分布等电极的微观结构参数也是决定电极及电池性能的关键因素。通过优化电极结构设计提升高比能电池的性能逐渐成为人们关注的焦点。本文综述了锂离子电池多孔电极结构设计优化的研究进展, 总结了多孔电极结构设计要素及制备方法, 最后对电极结构设计优化以及推动新型制备技术的规模化应用在高比能锂离子电池领域的未来发展前景进行展望。     

Research Progresses of Liquid Electrolytes in Lithium-Ion Batteries

In recent years, the rapid development of modern society is calling for advanced energy storage to meet the growing demands of energy supply and generation. As one of the most promising energy storage systems, secondary batteries are attracting much attention. The electrolyte is an important part of the secondary battery, and its composition is closely related to the electrochemical performance of the secondary batteries. Lithium-ion battery electrolyte is mainly composed of solvents, additives, and lithium salts, which are prepared according to specific proportions under certain conditions and according to the needs of characteristics. This review analyzes the advantages and current problems of the liquid electrolytes in lithium-ion batteries (LIBs) from the mechanism of action and failure mechanism, summarizes the research progress of solvents, lithium salts, and additives, analyzes the future trends and requirements of lithium-ion battery electrolytes, and points out the emerging opportunities in advanced lithium-ion battery electrolytes development.     

Recent Advances in Energy Chemical Engineering of Next-Generation Lithium Batteries

Rechargeable lithium-ion batteries (LIBs) afford a profound impact on our modern daily life. However, LIBs are approaching the theoretical energy density, due to the inherent limitations of intercalation chemistry; thus, they cannot further satisfy the increasing demands of portable electronics, electric vehicles, and grids. Therefore, battery chemistries beyond LIBs are being widely investigated. Next-generation lithium (Li) batteries, which employ Li metal as the anode and intercalation or conversion materials as the cathode, receive the most intensive interest due to their high energy density and excellent potential for commercialization. Moreover, significant progress has been achieved in Li batteries attributed to the increasing fundamental understanding of the materials and reactions, as well as to technological improvement. This review starts by summarizing the electrolytes for next-generation Li batteries. Key challenges and recent progress in lithium-ion, lithium–sulfur, and lithium–oxygen batteries are then reviewed from the perspective of energy and chemical engineering science. Finally, possible directions for further development in Li batteries are presented. Next-generation Li batteries are expected to promote the sustainable development of human civilization.     

New High Donor Electrolyte for Lithium–Sulfur Batteries

The unparalleled theoretical specific energy of lithium–sulfur (Li–S) batteries has attracted considerable research interest from within the battery community. However, most of the long cycling results attained thus far relies on using a large amount of electrolyte in the cell, which adversely affects the specific energy of Li–S batteries. This shortcoming originates from the low solubility of polysulfides in the electrolyte. Here, 1,3-dimethyl-2-imidazolidinone (DMI) is reported as a new high donor electrolyte for Li–S batteries. The high solubility of polysulfides in DMI and its activation of a new reaction route, which engages the sulfur radical (S₃^•−), enables the efficient utilization of sulfur as reflected in the specific capacity of 1595 mAh g⁻¹ under lean electrolyte conditions of 5 μL_electrolyte mg_sulfur⁻¹. Moreover, the addition of LiNO₃ stabilizes the lithium metal interface, thereby elevating the cycling performance to one of the highest known for high donor electrolytes in Li–S cells. These engineered high donor electrolytes are expected to advance Li–S batteries to cover a wide range of practical applications, particularly by incorporating established strategies to realize the reversibility of lithium metal electrodes.     

Polymer electrolytes and interfaces in solid-state lithium metal batteries

The polymer electrolyte based solid-state lithium metal batteries are the promising candidate for the high-energy electrochemical energy storage with high safety and stability. Moreover, the intrinsic properties of polymer electrolytes and interface contact between electrolyte and electrodes have played critical roles for determining the comprehensive performances of solid-state lithium metal batteries. In this review, the development of polymer electrolytes with the design strategies by functional units adjustments are firstly discussed. Then the interfaces between polymer electrolyte and cathode/anode, including the interface issues, remedy strategies for stabilizing the interface contact and reducing resistances, and the in-situ polymerization method for enhancing the compatibilities and assembling the batteries with favorable performances, have been introduced. Lastly, the perspectives on developing polymer electrolytes by functional units adjustment, and improving interface contact and stability by effective strategies for solid-state lithium metal batteries have been provided.     

Toward High-Energy-Density Lithium Metal Batteries: Opportunities and Challenges for Solid Organic Electrolytes

With increasing demands for safe, high capacity energy storage to support personal electronics, newer devices such as unmanned aerial vehicles, as well as the commercialization of electric vehicles, current energy storage technologies are facing increased challenges. Although alternative batteries have been intensively investigated, lithium (Li) batteries are still recognized as the preferred energy storage solution for the consumer electronics markets and next generation automobiles. However, the commercialized Li batteries still have disadvantages, such as low capacities, potential safety issues, and unfavorable cycling life. Therefore, the design and development of electromaterials toward high-energy-density, long-life-span Li batteries with improved safety is a focus for researchers in the field of energy materials. Herein, recent advances in the development of novel organic electrolytes are summarized toward solid-state Li batteries with higher energy density and improved safety. On the basis of new insights into ionic conduction and design principles of organic-based solid-state electrolytes, specific strategies toward developing these electrolytes for Li metal anodes, high-energy-density cathode materials (e.g., high voltage materials), as well as the optimization of cathode formulations are outlined. Finally, prospects for next generation solid-state electrolytes are also proposed.     

Creating Lithium‐Ion Electrolytes with Biomimetic Ionic Channels in Metal–Organic Frameworks

Solid‐state electrolytes are the key to the development of lithium‐based batteries with dramatically improved energy density and safety. Inspired by ionic channels in biological systems, a novel class of pseudo solid‐state electrolytes with biomimetic ionic channels is reported herein. This is achieved by complexing the anions of an electrolyte to the open metal sites of metal–organic frameworks (MOFs), which transforms the MOF scaffolds into ionic‐channel analogs with lithium‐ion conduction and low activation energy. This work suggests the emergence of a new class of pseudo solid‐state lithium‐ion conducting electrolytes.     

金属锂负极的关键技术与研究进展

综述了近几年科研工作者基于金属锂负极本身的改性的最新研究进展。金属锂的理论质量比容量达3860 mAh/g,密度为0.534 g/cm^3,标准还原电位为-3.045 V,这些优势使得金属锂成为下一代理想的锂二次电池(如锂硫、锂空气电池等)的负极材料。然而,锂离子的不均匀沉积导致的锂枝晶生长、体积膨胀及其随之带来的电池安全隐患和循环寿命的降低等缺陷严重困扰着金属锂电池的发展。本文从机械地增加锂负极的表面积、锂合金负极及混合锂负极、锂负极表面层以及二维三维基底四个方面对金属锂负极的改性进行分析。最后提出要实现金属锂电池的产业化,应从解决锂枝晶和体积膨胀两个方面,通过结合不同改性方法进行研究探索。