锂离子二次电池纳米复合聚合物电解质研究进展

聚合物锂离子电池具有重量轻，比能量高，安全性能好等优点，是本世纪发展的理想能源。锂离子电池用聚合物电解质的研究包括全固态聚合物电解质（SPE），凝胶聚合物电解质（GPE）和复合聚合物电解质（CPE）。本文重点综述了纳米复合聚合物电解质在锂离子电池中的应用研究进展及展望。     

锂离子二次电池固体电解质材料发展现状及展望

简述了锂离子二次电池的发展、组成及工作原理。重点介绍了锂离子二次电池中聚合物电解质分类,导电原理、性能以及发展方向。作为新型锂离子电池的电解质材料,聚合物电解质的性能较液体电解质有更大的发展潜力。     

全固态锂离子电池用PEO基聚合物电解质的研究进展

锂离子电池作为重要的能量储存元件在消费类电子产品、电动汽车和可再生能源存储等领域具有广泛的应用。传统液态电解质锂离子电池受到能量密度低、安全性差等诸多缺陷的限制,采用固态电解质替代液态电解质制备新型固态锂离子电池目前备受关注。PEO基固态聚合物电解质由于其设计简单、易于制造、使用安全等优点已被认为是替代传统液体电解质的首选。介绍了当前PEO基聚合物电解质的主要研究种类、特点和性能;阐述了锂离子在PEO基聚合物电解质中的导电机制;分析了与PEO络合的锂盐种类对聚合物电解质的电导率的影响规律;在此基础上提出了几种改善PEO基聚合物电解质性能的措施和方法。     

锂离子电池隔膜的研究与开发

介绍了锂离子电池隔膜材料的研究与进展，重点综述了聚烯烃锂离子电池隔膜材料的制备方法、孔径结构、孔隙率，透气率，自关闭性能等，认为多层复合隔膜既具有一定的强度又具有较低的自关闭温度，较适合作为锂离子电池隔膜，固体聚合物电解质在锂离子电池中作为电解质的同时还可以起隔膜的作用，表现出良好的应用前景。     

高安全性锂离子电池电解质研究进展

电解质是锂离子电池的重要组成部分,其电化学性能和热稳定性是影响电池安全性能的重要因素.简要介绍了商用锂离子电池电解质的性质以及由其引起的安全问题,从替代电解质材料和电解质添加剂两个方面综述了高安全性锂离子电池电解质的研究现状,着重阐述了离子液体、聚合物电解质、新型锂盐、成膜添加剂和阻燃添加剂等对锂离子电池安全性能提高的最新进展,展望了锂离子电解液的发展方向.     

锂离子电池用固体聚合物电解质的最新进展

全固态聚合物电解质由于其突出的安全性能,在锂离子电池中具有潜在的应用前景,其研究备受关注.本文综述了锂离子电池用全固态聚合物电解质的最新研究进展.主要关注的是电化学性能,尤其是室温附近的离子电导率.对性能较好的聚合物固体电解质体系进行了概述.     

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...     

用于锂离子电池的全固态聚合物电解质

用全氟醚作为增塑剂对PEO改性,并与双三氟甲烷磺酰亚胺锂复合,制备了全固态聚合物电解质。采用SEM、交流阻抗、稳态电流法及恒电流恒电压充放电等对固态聚合物电解质的性能进行了测试表征,结果表明:m(PFPE)∶m(PEO)=0.6的固态聚合物电解质膜的电导率30℃时为2.6×10-3 S·cm-1,同条件下电解质溶液电导为8.2×10-3 S·cm-1,二者处于同一个数量级;随PFPE的量增加,锂离子的迁移数增大;与液态电解质电池相比,固态聚合物电解质制成的电池具有更好的循环容量保持特性,固态聚合物电解质电池500次循环的容量保持率在88.1%,液态电解质电池循环容量保持率在64.5%左右;固态聚合电解质有很优异的耐高温安全性,在130℃和150℃下经1~2h热箱试验,用固态聚合物电解质制作的锂离子电池没出现明显体积变化,而相同条件下的液态电解质锂离子电池已发生爆裂或起火。     

有机硅在锂离子电池电解质中的应用

有机硅因其具有本身结构所决定的优异耐高温性和稳定性,将其应用于锂离子电池电解质中,可提高锂离子电池的安全性。综述了有机硅化合物在锂离子电池聚合物电解质和液态电解质中的应用形式及研究现状,包括作为聚合物电解质的组分、作为液态电解质的溶剂或添加剂,并详细介绍了作者所在研究团队近年来在锂离子电池含有机硅化合物电解质材料制备及研究方面的探索成果,同时探讨了其发展及应用前景。     

锂离子电池凝胶聚合物电解质制备工艺进展

凝胶聚合物电解质的应用广泛,在化学电源方面的应用主要集中应用于聚合物锂离子电池。本文介绍了锂离子电池用凝胶聚合物电解质的制备方法、各自的优缺点以及其在电池制备中的应用,重点介绍了UV固化技术在凝胶聚合物电解质制备中的应用,展望了聚合物锂离子电池UV聚合工艺的发展前景。     

聚合物固态电解质-锂负极界面的研究进展

固态锂电池是新能源领域最有希望的下一代高能量密度电池体系之一。本文以聚合物固态电解质-锂负极界面的构型特征和形成机理为基础, 系统讨论界面接触性、界面化学和电化学反应、锂负极枝晶生长等问题对二者之间的界面稳定性与兼容性的影响。基于此, 本文重点阐述了掺杂改性、结构设计等手段在三种聚合物基体与锂负极之间的界面的应用。此外, 本文还综述了常见界面表征手段及其在聚合物固态电解质-锂负极界面的应用情况。最后, 基于设计和构筑稳定的聚合物固态电解质-锂负极界面的相关策略, 本文对掺杂、核层设计等界面优化手段的发展前景进行分析与展望。     

Influence of Finely Dispersed Carbon Nanotubes on the Performance Characteristics of Polymer Electrolytes for Lithium Batteries

Electrospun membranes of poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP)/multiwall carbon nanotube (MWCNT) composite are prepared and loaded with lithium salts from electrolyte solution. Field emission transmission electron microscopy provides evidence for the uniform distribution of MWCNTs into the matrix of PVdF-HFP. The interconnected morphology as evident from field emission scanning electron micrograph forms the path for the lithium ion conduction. Results from electrochemical impedance spectroscopy inform that the presence of MWCNTs in PVdF-HFP matrix improves interfacial stability between lithium electrode and membrane and augment conduction path in the polymer electrolyte membrane. Further results from impedance measurement reveal the contribution of MWCNTs toward conductivity. A prototype cell is fabricated with PVdF-HFP/MWCNT as polymer electrolyte. The electrospun PVdF-HFP electrolyte membrane with 2% MWCNTs content shows an ionic conductivity of about 5.85 mSmiddotcm^-1 at 25 degC. Also, PVdF-HFP/MWCNT electrolyte membrane exhibits good electrochemical and interfacial stability and can be potentially suitable as electrolyte in lithium ion secondary battery     

Lithium garnets: Synthesis,structure, Li+ conductivity,Li+ dynamics and applications

Inorganic solid fast Li⁺ conductors based batteries are expected to overcome the limitations over safety concerns of flammable organic polymer electrolytes based Li⁺ batteries. Hence, an all-solid-state Li⁺ battery using non-flammable solid electrolyte have attracted much attention as next-generation battery. Therefore, in the development of all-solid-state lithium rechargeable batteries, it is important to search for a solid electrolyte material that has high Li⁺ conductivity, low electronic conductivity, fast charge transfer at the electrode interface and wide electrochemical window stability against potential electrodes and lithium metal. Hence, significant research effort must be directed towards developing novel fast Li⁺ conductors as electrolytes in all-solid-state lithium batteries. Among the reported inorganic solid Li⁺ conductive oxides, garnet-like structural compounds received considerable attention in recent times for potential application as electrolytes in all-solid-state lithium batteries. The focus of this review is to provide comprehensive overview towards the importance of solid fast lithium ion conductors, advantages of lithium garnets over other ceramic lithium ion conductors and understanding different strategies on synthesis of lithium garnets. Attempts have also been made to understand relationship between the structure, Li⁺ conduction and Li⁺ dynamics of lithium garnets. The status of lithium garnets as solid electrolyte in electrochemical devices like all-solid state lithium battery, lithium-air battery and sensor are also discussed.     

有机电解液在钠离子电池中的研究进展

随着对大型储能电池的需求逐渐增加,钠离子电池由于其资源丰富,价格低廉且与锂性质相似等优点而被广泛关注。在钠离子电池的关键材料选择中,钠离子电池的电化学性能和安全性同时受电解液的影响,这不仅决定了电池的电化学窗口和能量密度,而且还控制着电极/电解液界面的性质。本文首先综述了钠离子电池电解质的基本要求、主要分类,重点讨论了对钠离子电池电解质的选择性要求及不同钠盐的物化性能和对固体电解质界面的影响;其次针对不同溶剂和材料的兼容性以及材料在不同溶剂体系中的储能机制等,分别对材料在醚类和酯类电解液中获得的固体电解质界面特点、倍率性能、循环性能等展开分析。最后指出钠离子电池电解质未来在与材料的匹配、关键性表征方法等方面的发展路线。     

Advances and Prospects of Sulfide All‐Solid‐State Lithium Batteries via One‐to‐One Comparison with Conventional Liquid Lithium Ion Batteries

Owing to the safety issue of lithium ion batteries (LIBs) under the harsh operating conditions of electric vehicles and mobile devices, all‐solid‐state lithium batteries (ASSLBs) that utilize inorganic solid electrolytes are regarded as a secure next‐generation battery system. Significant efforts are devoted to developing each component of ASSLBs, such as the solid electrolyte and the active materials, which have led to considerable improvements in their electrochemical properties. Among the various solid electrolytes such as sulfide, polymer, and oxide, the sulfide solid electrolyte is considered as the most promising candidate for commercialization because of its high lithium ion conductivity and mechanical properties. However, the disparity in energy and power density between the current sulfide ASSLBs and conventional LIBs is still wide, owing to a lack of understanding of the battery electrode system. Representative developments of ASSLBs in terms of the sulfide solid electrolyte, active materials, and electrode engineering are presented with emphasis on the current status of their electrochemical performances, compared to those of LIBs. As a rational method to realizing high energy sulfide ASSLBs, the requirements for the sulfide solid electrolytes and active materials are provided along through simple experimental demonstrations. Potential future research directions in the development of commercially viable sulfide ASSLBs are suggested.     

PVDF-HFP基凝胶电解质用于LiNi0.5Co0.2Mn0.3O2三元正极锂离子电池

以聚偏氟乙烯-六氟丙烯(Poly(vinylidene fluoride-hexafluoropropylene),PVDF-HFP)为聚合物基体,新戊二醇二丙烯酸酯(Neopentyl glycol diacrylate,NPGDA)为交联剂,在引发剂偶氮二异丁腈(2,2′-Azobis(2-methylpropionitrile),AIBN)的作用下通过室温现场聚合法制备凝胶电解质用于锂离子电池。探索不同质量比PVDF-HFP/NPGDA对凝胶电解质性能和LiNi_(0.5)-Co_(0.2)Mn_(0.3)O_2三元正极锂离子电池性能的影响。结果表明,当质量比为1∶1时,凝胶电解质具有较高的离子电导率,为8.45mS·cm~(-1),锂离子迁移数为0.78,电化学窗口为4.5V。在电流密度30mA·g~(-1)恒流充放电,首次放电比容量为143mAh·g~(-1),循环50次后仍高达135.3mAh·g~(-1)。电流密度为300mA·g~(-1)时,放电比容量为100.2mAh·g~(-1)。     

锂磷氧氮电解质在无机薄膜锂电池中的应用

锂磷氧氮(LiPON,lithium phosphorous oxynitride)薄膜具有较高的离子电导率,极低的电子电导率,很宽的电化学稳定窗口等优点而成为全固态无机薄膜锂电池首选的电解质材料.简要介绍了LiPON薄膜的特性与制备方法,综述了国内外LiPON薄膜为电解质的薄膜锂电池的研究情况,并简要评述了目前薄膜锂电池制备中遇到的困难和今后的研究方向.     

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.     

Mass spectrometry investigations on electrolyte degradation products for the development of nanocomposite electrodes in lithium ion batteries

In the continuing challenge to find new routes to improve the performance of commercial lithium ion batteries cycling in alkyl carbonate-based electrolyte solutions, original designs, and new electrode materials are under active worldwide investigation. Our group has focused on the electrochemical behavior of a new generation of nanocomposite electrodes showing improved capacities (up to 3 times the capacity of conventional electrode materials). However, moving down to "nanometric-scale" active materials leads to a significant increase in electrolyte degradation, compared to that taking place within commercial batteries. Postmortem electrolyte studies on experimental coin cells were conducted to understand the degradation mechanisms. Structural analysis of the organic degradation products were investigated using a combination of complementary high-resolution mass spectrometry techniques: desorption under electron impact, electrospray ionization, and gas chromatography coupled to a mass spectrometer equipped with electron impact and chemical ionization ion sources. Numerous organic degradation products such as ethylene oxide oligomers (with methyl, hydroxyl, phosphate, and methyl carbonate endings) have been characterized. In light of our findings, possible chemical or electrochemical pathways are proposed to account for their formation. A thorough knowledge of these degradation mechanisms will enable us to propose new electrolyte formulations to optimize nanocomposite-based lithium ion battery performance.     

全固态锂离子电池中金属锂负极界面优化改性研究

以共聚物PEDOT-co-PEG作为锂金属阳极的表面改性层,采用磷酸铁锂复合阳极和“石榴石型”物质以及聚合氧乙烷聚合物组成的固体电解质制备了全固态锂离子电池。采用SEM分析了锂金属充电-放电反复操作后的形态学改变;采用电化学组抗谱试验研究了改性后的锂金属以及复合固体电解质接触面的稳定性并对全固态锂离子电池的充电-放电性能和界面稳定性进行了研究。结果表明,未改性的锂金属在固态电池充电-放电过程中会生成锂枝晶,从而导致全固态锂离子电池的高电流密度容量快速衰变;“石榴石型”物质以及聚合氧乙烷聚合物组成的固体电解质与改性后的金属锂具有良好的接触面,从而扼制锂枝晶的形成,提高全固态锂离子电池的机械性能;在PEDOT-co-PEG共聚物改性锂金属后,全固态锂离子电池的平稳性显著提高,且容量减弱放缓。