锂离子电池高容量硅负极嵌锂过程中的表面成膜研究

采用交流阻抗法、EDS与XPS成分分析对锂离子电池高容量硅负极在首次嵌锂过程中的表面成膜行为进行了研究, 并对膜组分进行了详细测试与分析. 交流阻抗分析发现硅负极的表面成膜现象出现在较低的嵌锂电位下, 膜厚随着嵌锂过程的进行而增加, 其组分以LiF和Li₂CO₃为主. 通过Ar离子流对硅负极表面的深度刻蚀的XPS分析发现, 其表面的膜层为非均质层, 暴露于电解液中一侧的膜层组分中碳酸盐含量较高, 而随着深度的增加, LiF的相对含量增加, 靠近电极一侧的膜层可能存在着少量硅的氧化物及其与电解液的反应产物. 少量Si由于不可逆反应形成的化合物也存在于SEI膜的膜层中.     

硅负极添加剂对锂离子电池的影响

选用乙炔黑(AB)、SuperP、VulcanXC-72和BP2000四种导电剂, 研究其物化性能及含量对硅电极电化学性能的影响; 探讨了粘合剂种类和用量对硅电极电化学性能的影响。采用场发射扫描电子显微镜对硅电极的形貌进行表征; 采用恒流充放电测试及循环伏安法对硅电极的电化学性能进行测试。结果表明, 导电剂SuperP具有良好的导电性、适中的比表面积(75.8 m²/g)和颗粒尺寸(39.2 nm), 有利于提高硅负极的循环性能及倍率循环性能。采用15wt%的导电剂 SuperP与15wt%的粘合剂CMC所制备的电极循环50次后可逆比容量保持在1143.8 mAh/g。     

锂离子电池多孔硅/碳复合负极材料的研究

以商业化多晶硅粉为原料, 采用金属银催化剂诱导化学腐蚀的方法制得三维多孔硅材料。通过优化腐蚀条件, 得到孔径约为130 nm, 比表面为4.85 m²/g的多孔硅材料。将多孔硅和PAN溶液混合球磨并经高温烧结后在多孔硅表面包覆上一层致密的无定形碳膜, 从而制得多孔硅/碳复合材料作为锂离子电池的负极材料。3D多孔硅结构可以缓解电化学嵌/脱锂过程中材料的体积效应, 无定形碳膜层可有效改善复合材料的导电性能。电化学性能测试表明, 该多孔硅/碳复合负极材料电池在0.4 A/g的恒电流下, 首次放电容量3345 mAh/g, 首次循环库伦效率85.8%, 循环55次后容量仍保持有1645 mAh/g。并且在4 A/g的倍率下, 容量仍维持有1174 mAh/g。该方法原料成本低廉, 可规模化生产。     

Silicon‐Based Anodes for Lithium‐Ion Batteries: From Fundamentals to Practical Applications

Silicon has been intensively studied as an anode material for lithium‐ion batteries (LIB) because of its exceptionally high specific capacity. However, silicon‐based anode materials usually suffer from large volume change during the charge and discharge process, leading to subsequent pulverization of silicon, loss of electric contact, and continuous side reactions. These transformations cause poor cycle life and hinder the wide commercialization of silicon for LIBs. The lithiation and delithiation behaviors, and the interphase reaction mechanisms, are progressively studied and understood. Various nanostructured silicon anodes are reported to exhibit both superior specific capacity and cycle life compared to commercial carbon‐based anodes. However, some practical issues with nanostructured silicon cannot be ignored, and must be addressed if it is to be widely used in commercial LIBs. This Review outlines major impactful work on silicon‐based anodes, and the most recent research directions in this field, specifically, the engineering of silicon architectures, the construction of silicon‐based composites, and other performance‐enhancement studies including electrolytes and binders. The burgeoning research efforts in the development of practical silicon electrodes, and full‐cell silicon‐based LIBs are specially stressed, which are key to the successful commercialization of silicon anodes, and large‐scale deployment of next‐generation high energy density LIBs.     

锂离子电池炭负极材料结构及嵌锂机理研究进展

炭材料取代金属锂作为负极后,锂离子电池在商业应用上取得了成功,并以其高能量密度在各种电子设备上广泛使用.锂离子电池的性能很大程度上取决于炭负极材料的微观结构,不同种类的炭材料其电化学性能有很大差别.对近几年所研究的可逆储锂炭材料进行了综述,着重总结了炭负极材料的种类、结构及其嵌锂机理,并展望了锂离子电池炭负极材料的研究进展.     

Dual‐Functionalized Double Carbon Shells Coated Silicon Nanoparticles for High Performance Lithium‐Ion Batteries

To address the challenge of huge volume change and unstable solid electrolyte interface (SEI) of silicon in cycles, causing severe pulverization, this paper proposes a “double‐shell” concept. This concept is designed to perform dual functions on encapsulating volume change of silicon and stabilizing SEI layer in cycles using double carbon shells. Double carbon shells coated Si nanoparticles (DCS‐Si) are prepared. Inner carbon shell provides finite inner voids to allow large volume changes of Si nanoparticles inside of inner carbon shell, while static outer shell facilitates the formation of stable SEI. Most importantly, intershell spaces are preserved to buffer volume changes and alleviate mechanical stress from inner carbon shell. DCS‐Si electrodes display a high rechargeable specific capacity of 1802 mAh g⁻¹ at a current rate of 0.2 C, superior rate capability and good cycling performance up to 1000 cycles. A full cell of DCS‐Si//LiNi_0.45Co_0.1Mn_1.45O₄ exhibits an average discharge voltage of 4.2 V, a high energy density of 473.6 Wh kg⁻¹, and good cycling performance. Such double‐shell concept can be applied to synthesize other electrode materials with large volume changes in cycles by simultaneously enhancing electronic conductivity and controlling SEI growth.     

A Quadruple‐Hydrogen‐Bonded Supramolecular Binder for High‐Performance Silicon Anodes in Lithium‐Ion Batteries

With extremely high specific capacity, silicon has attracted enormous interest as a promising anode material for next‐generation lithium‐ion batteries. However, silicon suffers from a large volume variation during charge/discharge cycles, which leads to the pulverization of the silicon and subsequent separation from the conductive additives, eventually resulting in rapid capacity fading and poor cycle life. Here, it is shown that the utilization of a self‐healable supramolecular polymer, which is facilely synthesized by copolymerization of tert‐butyl acrylate and an ureido‐pyrimidinone monomer followed by hydrolysis, can greatly reduce the side effects caused by the volume variation of silicon particles. The obtained polymer is demonstrated to have an excellent self‐healing ability due to its quadruple‐hydrogen‐bonding dynamic interaction. An electrode using this self‐healing supramolecular polymer as binder exhibits an initial discharge capacity as high as 4194 mAh g⁻¹ and a Coulombic efficiency of 86.4%, and maintains a high capacity of 2638 mAh g⁻¹ after 110 cycles, revealing significant improvement of the electrochemical performance in comparison with that of Si anodes using conventional binders. The supramolecular binder can be further applicable for silicon/carbon anodes and therefore this supramolecular strategy may increase the choice of amendable binders to improve the cycle life and energy density of high‐capacity Li‐ion batteries.     

静电纺丝在高效可逆离子电池储能中的应用

高效、稳定、低成本可逆离子电池的研究对大型能源存储、便携电子设备、电动汽车、航空航天以及生态环境等领域的发展有着重大意义。可逆离子电池电极材料的微纳设计与结构调控是其高性能化的重要途径。静电纺丝制备功能微纳电极材料具有以下优势:(1)一维构筑单元有利于电子快速传导;(2)微纳化构筑单元具有短的离子扩散距离和高电极/电解液接触比表面积;(3)三维网络骨架结构可有效降低电极结构破坏。同时,通过调节静电纺丝体系参数可实现电极材料的结构、组分、尺寸、表面修饰、掺杂等参量可控制备。非金属(如Si、Ge)、金属(如Sn、Sb)以及过渡金属氧化物(如SnO_2、Fe_2O_3、Co_3O_4)、金属硫化物(如MoS_2、Co_9S_8)负极材料以及磷酸盐(如LiFePO_4、Li_3V_2(PO_4)_3)因具有高的理论比容量和能量密度等优点而被广泛地应用于超级电容器、离子电池(锂离子电池、钠离子电池、锂硫电池)等新一代储能器件中。然而,低导电性、高体积膨胀率等使得这类材料的倍率性能和使用寿命极大降低,制约了它们的商业化应用前景。基于碳材料(非晶碳、碳纳米管、石墨烯)以及导电聚合物设计制备不同微纳结构的碳基和聚合物基复合材料可有效解决以上难题,提高其储能性能。静电纺丝技术可以通过设计纺丝装置,调控纺丝前驱液的浓度,结合超声磁力搅拌促进纳米颗粒均匀分散以及高温热解等参量调控,有效制备得到自支撑纺丝碳基纤维复合材料。近年来,基于静电纺丝制备的柔性自支撑结构材料被广泛应用于能源存储领域,包括超级电容器、隔膜材料、离子电池等。然而,不同聚合物静电纺丝条件有较大差异,主要由聚合物的分子量大小、带电基团分布、亲疏水性、溶剂、溶液粘度等参量所决定。聚合物静电纺丝的前驱液主要为水溶性高分子与非水溶性高分子,溶剂通常为N,N-二甲基甲酰胺、乙醇等。聚合物与金属盐常被用于静电纺丝制备微纳复合纤维材料,通过调节纺丝参量(如聚合物溶液粘度、溶剂种类、电压、针尖与接收装置之间的距离、聚合物输运速率、温度以及湿度等)对其结构特性进行精确调控,实现储能容量和稳定性的双提升。本文将主要从以下几个方面介绍静电纺丝在可逆离子电池储能中的应用:静电纺丝技术进展,静电纺丝微纳材料在可逆离子电池中的应用,以及该领域研究的总结与展望。     

Self-Repairable Silicon Anodes Using a Multifunctional Binder for High-Performance Lithium-Ion Batteries

Despite of extremely high theoretical capacity of Si (3579 mAh g⁻¹), Si anodes suffer from pulverization and delamination of the electrodes induced by large volume change during charge/discharge cycles. To address those issues, herein, self-healable and highly stretchable multifunctional binders, polydioxythiophene:polyacrylic acid:phytic acid (PEDOT:PAA: PA, PDPP) that provide Si anodes with self-healability and excellent structural integrity is designed. By utilizing the self-healing binder, Si anodes self-repair cracks and damages of Si anodes generated during cycling. For the first time, it is demonstrated that Si anodes autonomously self-heal artificially created cracks in electrolytes under practical battery operating conditions. Consequently, this self-healable Si anode can still deliver a reversible capacity of 2312 mAh g⁻¹ after 100 cycles with remarkable initial Coulombic efficiency of 94%, which is superior to other reported Si anodes. Moreover, the self-healing binder possesses enhanced Li-ion diffusivity with additional electronic conductivity, providing excellent rate capability with a capacity of 2084 mAh g⁻¹ at a very high C-rate of 5 C.     

锂离子电池碳负极材料结构与性能的关系

论述了目前锂离子电池碳负极材料的研究概况,并且对碳材料的结构特点进行分类;阐述了影响锂离子碳负极 材料结构因素。同时简述了碳材料表面修饰２对碳负极嵌锂性能的影响,评价了各种表面修饰方法的优缺点。     

Silicon Decorated Cone Shaped Carbon Nanotube Clusters for Lithium Ion Battery Anodes

In this work, we report the synthesis of an three‐dimensional (3D) cone‐shape CNT clusters (CCC) via chemical vapor deposition (CVD) with subsequent inductively coupled plasma (ICP) treatment. An innovative silicon decorated cone‐shape CNT clusters (SCCC) is prepared by simply depositing amorphous silicon onto CCC via magnetron sputtering. The seamless connection between silicon decorated CNT cones and graphene facilitates the charge transfer in the system and suggests a binder‐free technique of preparing lithium ion battery (LIB) anodes. Lithium ion batteries based on this novel 3D SCCC architecture demonstrates high reversible capacity of 1954 mAh g^?1 and excellent cycling stability (>1200 mAh g^?1 capacity with ≈100% coulombic efficiency after 230 cycles).     

Graphene Caging Silicon Particles for High‐Performance Lithium‐Ion Batteries

Silicon holds great promise as an anode material for lithium‐ion batteries with higher energy density; its implication, however, is limited by rapid capacity fading. A catalytic growth of graphene cages on composite particles of magnesium oxide and silicon, which are made by magnesiothermic reduction reaction of silica particles, is reported herein. Catalyzed by the magnesium oxide, graphene cages can be conformally grown onto the composite particles, leading to the formation of hollow graphene‐encapsulated Si particles. Such materials exhibit excellent lithium storage properties in terms of high specific capacity, remarkable rate capability (890 mAh g^?1 at 5 A g^?1), and good cycling retention over 200 cycles with consistently high coulombic efficiency at a current density of 1 A g^?1. A full battery test using LiCoO₂ as the cathode demonstrates a high energy density of 329 Wh kg^?1.     

锂离子电池磷酸铁锂正极材料的制备及改性研究进展

橄榄石型磷酸铁锂(LiFePO4)由于安全性能好、循环寿命长、原材料来源广泛、无环境污染等优点被公认为是最具发展潜力的锂离子动力与储能电池正极材料。综述了近年来磷酸铁锂正极材料在制备和改性方面的最新进展。在此基础上,提出了磷酸铁锂正极材料未来的主要研究和发展方向。     

Low‐Temperature Growth of All‐Carbon Graphdiyne on a Silicon Anode for High‐Performance Lithium‐Ion Batteries

In situ weaving an all‐carbon graphdiyne coat on a silicon anode is scalably realized under ultralow temperature (25 °C). This economical strategy not only constructs 3D all‐carbon mechanical and conductive networks with reasonable voids for the silicon anode at one time but also simultaneously forms a robust interfacial contact among the electrode components. The intractable problems of the disintegrations in the mechanical and conductive networks and the interfacial contact caused by repeated volume variations during cycling are effectively restrained. The as‐prepared electrode demostrates the advantages of silicon regarding capacity (4122 mA h g^?1 at 0.2 A g^?1) with robust capacity retention (1503 mA h g^?1) after 1450 cycles at 2 A g^?1, and a commercial‐level areal capacity up to 4.72 mA h cm^?2 can be readily approached. Furthermore, this method shows great promises in solving the key problems in other high‐energy‐density anodes.     

物理气相沉积制备锂离子电池正极薄膜研究进展

薄膜锂离子电池是锂离子电池发展的最新领域,正极材料的薄膜化是薄膜锂离子电池的重要部分.综述了近年来国内外物理气相沉积在薄膜锂离子电池正极薄膜方面的研究新进展,着重介绍了射频磁控溅射、脉冲激光沉积、电子束沉积等制备技术的工作原理、特点及发展,并对这些制备技术在锂离子电池正极薄膜制备中的应用进行了分析、比较和评价.