钡含量对新型石榴石结构固态电解质导电性能的影响

用传统固相烧结法制备试样并研究钡含量对电导率的影响。综合运用XRD、SEM、EIS和密度测试对试样进行表征。XRD衍射分析表明,合成物质基本为石榴石结构,当钡含量过多时,出现二次相。立方晶格常数随着钡含量的增大而增大,当X>1时,变化无规律。测试了试样在20~250℃范围内的交流阻抗,实验结果表明,电导率随着X的增大而增大,并在X=1时达到最大值(8.77×10-6S/cm,20℃),继续增大X电导率反而降低。活化能随着X的增大而减小,并在X=1时达到最小值(0.41eV),X继续增大活化能反而增大。Li6BaLa2Ta2O12的SEM照片中烧结粉末颗粒不均匀,有团聚现象,相对密度为80.7%。     

石墨烯/锂金属复合材料的制备和电化学性能

对于高能量密度锂金属电池体系,安全、稳定的锂负极材料是关键。采用微波还原、热还原和机械剥离方法制备了3种具有不同形貌结构的石墨烯,并通过压制和叠层工艺,制备出石墨烯/锂金属复合材料。通过扫描电子显微镜(SEM)、拉曼(Raman)、X射线光电子能谱(XPS)和N₂吸脱附曲线分析了不同石墨烯材料的形貌、组成、结构以及石墨烯/锂金属复合材料的形貌。同时采用Li||Li对称电池和LiFeO₄全电池,评价了石墨烯/锂金属复合材料作为负极的电化学性能。结果表明,石墨烯/锂金属复合材料具有层状结构,在微波还原石墨烯(MRGO)、热还原石墨烯(RGO)和机械剥离石墨烯(EG)中,MRGO最适用于改性金属锂,叠层3次得到的4MRGO/3Li复合材料具有最优的电化学性能。基于4MRGO/3Li的Li||Li对称电池在9.9 mV左右的极化电压下稳定循环1200圈,相对于纯锂金属,极化电压降低10.6 mV,安全性和稳定性大大提升。以4MRGO/3Li复合材料为负极的LiFeO₄全电池稳定循环800圈后,放电容量保持为156 mAh/g。     

应用于全固态锂电池的复合固态电解质研究进展

基于固态电解质和锂金属负极的全固态锂离子电池能量密度高、 安全性好,能够有效地抑制锂枝晶生长并改善电池的本征安全性.固态电解质作为全固态电池的关键材料,成为近年来的研究热点.目前,通过在聚合物基体中添加无机填料得到的复合固态电解质具有优异的力学性能和电化学性能,实现了对单一固态电解质体系的"取长补短",被视为最具前景的...     

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。     

锂金属电池中复合固态电解质与负极界面的研究进展

与传统锂离子电池相比,全固态锂金属电池因其安全性好、能量密度高的特点备受关注.但是电极与固态电解质的固固接触带来较大的界面阻抗,而锂金属较为活泼易与固态电解质发生反应,造成了界面不稳定.界面问题已经成为制约全固态电池发展的关键因素之一.有机-无机复合固态电解质兼顾无机固态电解质和有机固态电解质的优势,具有较高离子电导率和一定的力学强度,展现出优异的实用化前景.本文综述了近年来复合固态电解质与金属锂负极界面改性的研究进展,总结了当前界面改性的主要研究思路:包括在界面构筑"软接触"、调节固态电解质的力学性能以及调控界面处锂离子的沉积动力学过程等.同时,也对今后界面改性的研究趋势进行了展望.     

人造固态电解质界面在锂金属负极保护中的应用研究EI北大核心CSCD

锂金属具有最低的氧化还原电位(-3.04V vs标准氢电极)和极高的比容量(3860mAh·g^-1),是理想的锂二次电池负极材料.然而电化学循环过程中,由于锂的不均匀成核生长,其表面产生锂枝晶,锂枝晶持续生长会刺穿隔膜,造成电池短路甚至引发火灾.因此需要对锂金属负极进行保护,抑制负面问题,发挥高性能.人造固态电解质界面技术是一种有效的锂金属负极保护策略,本质是预先在锂金属表面涂覆上保护层,保护层具有较高的离子传导性和电化学稳定性、较好的阻隔性和机械强度,可得到高效率、长寿命和无枝晶的锂金属负极.本文将近年来人造固态电解质界面在锂金属负极保护中的研究进展进行综述,对其制备方法、结构特点、锂金属负极循环性能、全电池电化学性能等方面作了详细介绍,分析当前存在问题并指出锂金属负极研究不仅需要加深机理研究还得与实际应用相结合.     

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.     

全固态锂离子电池正极与石榴石型固体电解质界面的研究进展

全固态锂离子电池具有高安全性、高能量密度、宽使用温度范围以及长使用寿命等优势, 在动力电池汽车和大规模储能电网领域具有广阔的应用前景。作为全固态电池的重要组成部分, 无机固体电解质尤其是石榴石型固态电解质在室温下锂离子电导率可达10 ^-3 S·cm ^-1, 且对金属锂相对稳定, 在全固态电池的应用中具有明显的优势。然而正极与石榴石型固体电解质间接触性能以及界面的稳定性差, 使得电池表现出高的界面阻抗、低的库伦效率和差的循环性能。本文以全固态锂离子电池正极与石榴石型固体电解质界面为研究对象, 分析了正极/固体电解质的界面特性以及界面研究中存在的问题, 综述了正极复合、界面处理工艺、界面层引入等界面调控和改性的方法, 阐述了优化正极与石榴石型固体电解质界面结构, 改善界面润湿性的解决思路, 提出了未来全固态锂离子电池发展中有待进一步改进的关键问题, 为探索全固态锂离子电池的实际应用提供了借鉴。     

煅烧温度对Li0.33La0.56TiO3固态离子电容器性能的影响

本文采用固相法在900、1000、1100和1200℃煅烧温度条件下合成了Li_0.33La_0.56TiO₃(LLTO)固态电解质材料, 并将其组装为LLTO固态离子电容器。采用X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、电化学阻抗谱(EIS)和循环伏安法(CV)等技术研究了煅烧温度对LLTO固态电解质和固态离子电容器的显微结构、形貌、离子电导率和储能性能的影响。实验表明, 较高的煅烧温度有利于获得性能优异的LLTO固态离子电容器。在室温下, 1200℃煅烧温度制备的固态离子电容器晶粒离子电导率高达 9.6×10^-4 S/cm, 且具有明显的双电层电容特性, 在4 V电压窗口下比电容为3.52 mF/g。此外, 固态离子电容器比电容随晶粒电导率的增大而增大, 同时受电极与固态电解质接触面积的影响。     

合成温度对Li2FeSiO4／C电化学性能的影响

采用球磨掺碳及固相法合成锂离子电池正极材料Li2FeSiO4/C,研究了合成温度对材料结构和电化学性能的影响.用X射线衍射(XRD)、扫描电镜(SEM)对材料的结构与形貌进行了表征;并对不同焙烧温度下合成的Li2FeSiO4/C材料的电化学性能进行了研究.结果表明,650℃合成的Li:FeSiO4/C电化学性能最佳,在C/16的倍率下首次放电容量达到144.8mAh/g,10次循环后容量仍保持有136.5mAh/g.     

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.     

Composition Modulation and Structure Design of Inorganic‐in‐Polymer Composite Solid Electrolytes for Advanced Lithium Batteries

Owing to their safety, high energy density, and long cycling life, all‐solid‐state lithium batteries (ASSLBs) have been identified as promising systems to power portable electronic devices and electric vehicles. Developing high‐performance solid‐state electrolytes is vital for the successful commercialization of ASSLBs. In particular, polymer‐based composite solid electrolytes (PCSEs), derived from the incorporation of inorganic fillers into polymer solid electrolytes, have emerged as one of the most promising electrolyte candidates for ASSLBs because they can synergistically integrate many merits from their components. The development of PCSEs is summarized. Their major components, including typical polymer matrices and diverse inorganic fillers, are reviewed in detail. The effects of fillers on their ionic conductivity, mechanical strength, thermal/interfacial stability and possible Li⁺‐conductive mechanisms are discussed. Recent progress in a number of rationally constructed PCSEs by compositional and structural modulation based on different design concepts is introduced. Successful applications of PCSEs in various lithium‐battery systems including lithium–sulfur and lithium–gas batteries are evaluated. Finally, the challenges and future perspectives for developing high‐performance PCSEs are proposed.     

Synthesis and Properties of a Photopatternable Lithium‐Ion Conducting Solid Electrolyte

One of the important considerations for the development of on‐chip batteries is the need to photopattern the solid electrolyte directly on electrodes. Herein, the photopatterning of a lithium‐ion conducting solid electrolyte is demonstrated by modifying a well‐known negative photoresist, SU‐8, with LiClO₄. The resulting material exhibits a room temperature ionic conductivity of 52 µS cm^?1 with a wide electrochemical window (>5 V). Half‐cell galvanostatic testing of 3 µm thin films spin‐coated on amorphous silicon validates its use for on‐chip energy‐storage applications. The modified SU‐8 possesses excellent mechanical integrity, is thermally stable up to 250 °C, and can be photopatterned with micrometer‐scale resolution. These results present a promising direction for the integration of electrochemical energy storage in microelectronics.     

Carbon Nanotube–CoF2 Multifunctional Cathode for Lithium Ion Batteries: Effect of Electrolyte on Cycle Stability

Transition metal fluorides (MF_x) offer remarkably high theoretical energy density. However, the low cycling stability, low electrical and ionic conductivity of metal fluorides have severely limited their applications as conversion‐type cathode materials for lithium ion batteries. Here, a scalable and low‐cost strategy is reported on the fabrication of multifunctional cobalt fluoride/carbon nanotube nonwoven fabric nanocomposite, which demonstrates a combination of high capacity (near‐theoretical, ) and excellent mechanical properties. Its strength and modulus of toughness exceed that of many aluminum alloys, cast iron, and other structural materials, fulfilling the use of MF_x‐based materials in batteries with load‐bearing capabilities. In the course of this study, cathode dissolution in conventional electrolytes has been discovered as the main reason that leads to the rapid growth of the solid electrolyte interphase layer and attributes to rapid cell degradation. And such largely overlooked degradation mechanism is overcome by utilizing electrolyte comprising a fluorinated solvent, which forms a protective ionically conductive layer on the cathode and anode surfaces. With this approach, 93% capacity retention is achieved after 200 cycles at the current density of 100 mA g⁻¹ and over 50% after 10 000 cycles at the current density of 1000 mA g⁻¹.     

Reviving Lithium‐Metal Anodes for Next‐Generation High‐Energy Batteries

Lithium‐metal batteries (LMBs), as one of the most promising next‐generation high‐energy‐density storage devices, are able to meet the rigid demands of new industries. However, the direct utilization of metallic lithium can induce harsh safety issues, inferior rate and cycle performance, or anode pulverization inside the cells. These drawbacks severely hinder the commercialization of LMBs. Here, an up‐to‐date review of the behavior of lithium ions upon deposition/dissolution, and the failure mechanisms of lithium‐metal anodes is presented. It has been shown that the primary causes consist of the growth of lithium dendrites due to large polarization and a strong electric field at the vicinity of the anode, the hyperactivity of metallic lithium, and hostless infinite volume changes upon cycling. The recent advances in liquid organic electrolyte (LOE) systems through modulating the local current density, anion depletion, lithium flux, the anode–electrolyte interface, or the mechanical strength of the interlayers are highlighted. Concrete strategies including tailoring the anode structures, optimizing the electrolytes, building artificial anode–electrolyte interfaces, and functionalizing the protective interlayers are summarized in detail. Furthermore, the challenges remaining in LOE systems are outlined, and the future perspectives of introducing solid‐state electrolytes to radically address safety issues are presented.     

Self‐Suppression of Lithium Dendrite in All‐Solid‐State Lithium Metal Batteries with Poly(vinylidene difluoride)‐Based Solid Electrolytes

Polymer‐based electrolytes have attracted ever‐increasing attention for all‐solid‐state lithium (Li) metal batteries due to their ionic conductivity, flexibility, and easy assembling into batteries, and are expected to overcome safety issues by replacing flammable liquid electrolytes. However, it is still a critical challenge to effectively block Li dendrite growth and improve the long‐term cycling stability of all‐solid‐state batteries with polymer electrolytes. Here, the interface between novel poly(vinylidene difluoride) (PVDF)‐based solid electrolytes and the Li anode is explored via systematical experiments in combination with first‐principles calculations, and it is found that an in situ formed nanoscale interface layer with a stable and uniform mosaic structure can suppress Li dendrite growth. Unlike the typical short‐circuiting that often occurs in most studied poly(ethylene oxide) systems, this interface layer in the PVDF‐based system causes an open‐circuiting feature at high current density and thus avoids the risk of over‐current. The effective self‐suppression of the Li dendrite observed in the PVDF–LiN(SO₂F)₂ (LiFSI) system enables over 2000 h cycling of repeated Li plating–stripping at 0.1 mA cm^?2 and excellent cycling performance in an all‐solid‐state LiCoO₂||Li cell with almost no capacity fade after 200 cycles at 0.15 mA cm^?2 at 25 °C. These findings will promote the development of safe all‐solid‐state Li metal batteries.     

Early Lithium Plating Behavior in Confined Nanospace of 3D Lithiophilic Carbon Matrix for Stable Solid‐State Lithium Metal Batteries

Considerable efforts are devoted to relieve the critical lithium dendritic and volume change problems in the lithium metal anode. Constructing uniform Li⁺ distribution and lithium “host” are shown to be the most promising strategies to drive practical lithium metal anode development. Herein, a uniform Li nucleation/growth behavior in a confined nanospace is verified by constructing vertical graphene on a 3D commercial copper mesh. The difference of solid‐electrolyte interphase (SEI) composition and lithium growth behavior in the confined nanospace is further demonstrated by in‐depth X‐ray photoelectron spectrometer (XPS) and line‐scan energy dispersive X‐ray spectroscopic (EDS) methods. As a result, a high Columbic efficiency of 97% beyond 250 cycles at a current density of 2 mA cm^?2 and a prolonged lifespan of symmetrical cell (500 cycles at 5 mA cm^?2) can be easily achieved. More meaningfully, the solid‐state lithium metal cell paired with the composite lithium anode and LiNi_0.5Co_0.2Mn_0.3O₂ (NCM) as the cathode also demonstrate reduced polarization and extended cycle. The present confined nanospace–derived hybrid anode can further promote the development of future all solid‐state lithium metal batteries.     

A Flexible Ceramic/Polymer Hybrid Solid Electrolyte for Solid-State Lithium Metal Batteries

Ceramic/polymer hybrid solid electrolytes (HSEs) have attracted worldwide attentions because they can overcome defects by combining the advantages of ceramic electrolytes (CEs) and solid polymer electrolytes (SPEs). However, the interface compatibility of CEs and SPEs in HSE limits their full function to a great extent. Herein, a flexible ceramic/polymer HSE is prepared via in situ coupling reaction. Ceramic and polymer are closely combined by strong chemical bonds, thus the problem of interface compatibility is resolved and the ions can transport rapidly by an expressway. The as-prepared membrane demonstrates an ionic conductivity of 9.83 × 10⁻⁴ S cm⁻¹ at room temperature and a high Li⁺ transference numbers of 0.68. This in situ coupling reaction method provides an effective way to resolve the problem of interface compatibility.     

Overcoming the Interfacial Limitations Imposed by the Solid–Solid Interface in Solid‐State Batteries Using Ionic Liquid‐Based Interlayers

Li‐garnets are promising inorganic ceramic solid electrolytes for lithium metal batteries, showing good electrochemical stability with Li anode. However, their brittle and stiff nature restricts their intimate contact with both the electrodes, hence presenting high interfacial resistance to the ionic mobility. To address this issue, a strategy employing ionic liquid electrolyte (ILE) thin interlayers at the electrodes/electrolyte interfaces is adopted, which helps overcome the barrier for ion transport. The chemically stable ILE improves the electrodes‐solid electrolyte contact, significantly reducing the interfacial resistance at both the positive and negative electrodes interfaces. This results in the more homogeneous deposition of metallic lithium at the negative electrode, suppressing the dendrite growth across the solid electrolyte even at high current densities of 0.3 mA cm^?2. Further, the improved interface Li/electrolyte interface results in decreasing the overpotential of symmetric Li/Li cells from 1.35 to 0.35 V. The ILE modified Li/LLZO/LFP cells stacked either in monopolar or bipolar configurations show excellent electrochemical performance. In particular, the bipolar cell operates at a high voltage (≈8 V) and delivers specific capacity as high as 145 mAh g^?1 with a coulombic efficiency greater than 99%.