基于工业废料的Si/TiN/TiSi2多相复合锂离子电池负极材料的制备及其电化学性能

Si负极材料理论容量高,但其电子电导率低和脱嵌锂过程体积变化大易粉化,使其循环稳定性和倍率性能差以及高性能硅基锂离子电池负极材料成本高,这均妨碍了其大规模产业化应用.本研究提出以太阳能电池硅片切割废料Si粉和TiN粉为原材料,采用低成本的活性气体机械球磨法制备了一种高性能的Si/TiN/TiSi2多相复合负极储锂材料.研究发现,Si在H2气氛球磨过程中与部分TiN发生反应,原位生成了纳米尺度的TiSi2,TiN和新形成的TiSi2弥散于亚微米尺度的Si基体中.Si/TiN/TiSi2复合材料的电化学性能与TiN的添加量紧密相关.其中,物质的量比Si/0.2TiN的体系具有最佳的电化学性能,在300 mA·g-1电流密度下,其首次可逆容量为2394 mA·h·g-1,首次库伦效率达75.8％,经过200次循环后,容量仍保持1295 mA·h·g-1,保持率高达54％.在2.0 A·g-1电流密度下的可逆容量达到609 mA·h·g-1.机理分析表明:高导电的惰性相TiSi2和TiN弥散在Si基体中不仅有利于电极材料在充放电循环过程中的电子传输,且有效缓冲了Si在嵌脱锂过程的巨大体积变化.这是TiN添加改善硅基复合负极材料电化学性能的主要原因.     

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。     

锂离子电池中的高容量合金/碳复合电极研究

采用含有多碳链结构的金属有机化合物,利用固相反应,得到亚微米尺寸的SnSbx合金颗粒,高度均匀地沉积在中间相碳微球(CMS)球体表面.合成的SnSb_x/CMS复合材料做成扣式电池经电化学性能测试,电极可逆比容量超过430mAhg^-1,相对于空白CMS电极(可逆比容量310mAhg^-1)提高近40％,循环30次后容量维持在90％以上.结果表明:制备的复合电极不但具有较高的可逆比容量,而且能防止纯粹合金嵌脱锂过程产生的严重体积效应,从而提高电极循环性能.     

钠离子电池Sb基负极材料的研究进展

作为钠离子电池负极材料的一种,Sb基负极材料拥有比碳材料更高的理论比容量和低成本的优势,极具商业化应用前景,受到研究者们的密切关注。尽管Sb金属单质具有安全性能好、合成方便等诸多优点,但该电极材料在反复充放电过程中存在以下问题:(1)较大的体积膨胀,极易引起钠离子的不可逆脱嵌,从而导致充放电效率较低;(2)晶体结构易坍塌,材料粉化严重,从而造成电极材料长周期循环稳定性差,容量大幅衰减。研究者们通过调控Sb金属单质的粒径、形貌和结构等手段,显著改善了其电化学性能。即便如此,仍然无法有效解决Sb金属单质在循环过程中因体积膨胀造成的充放电效率低和容量迅速衰减的问题。为了解决这一问题,人们设计开发了Sb/C复合材料以及Sb基化合物材料。Sb/C复合材料利用碳材料良好的柔韧性、优异的导电性以及形貌和结构皆可调控等优势,在一定程度上改善了改性后电极材料的循环性能。Sb合金材料是由活性金属Sb和其他活性金属或非活性金属合金化而成,体积效应得到抑制,放电容量提高。Sb氧化物和Sb硫化物等Sb的非金属化合物材料反应机理为合金化反应和转化反应机理共存,均可贡献容量,因而此类材料具有较高的比容量。为同时达到改善材料结构性能和抑制体积膨胀的目的,可通过构筑结构较为复杂但电化学性能优异的Sb的其他复合物材料。本文对比分析了不同Sb基材料的储钠机理、性能特点、存在的问题以及电化学性能的优化方法。同时指出单一的改性方法并不能显著提升材料的性能,而结构优化、合金成分控制以及优选还原剂、粘结剂和电解质添加剂等多元改性工艺的综合设计,可以更有效地改善Sb基负极材料的电化学性能,最后提出现阶段Sb基材料作为钠离子电池负极材料所面临的挑战及未来商业化应用前景。     

Si基锂离子电池负极材料的纳米化和合金化

Si作为一种新型锂离子电池负极材料,具有理论比容量高、来源丰富、成本低廉、安全性能好等优点,近年来备受关注。但其在充放电过程中会产生巨大的体积变化而使得材料粉化严重,导致循环过程中容量迅速衰退,难以满足实用化的需求。纳米化和合金化是改善Si负极材料的有效途径,纳米化能够有效缓解材料嵌脱锂过程中体积变化造成的机械应力、缩短锂离子的迁移距离,从而明显改善Si基材料的电化学循环稳定性能;合金化可以减小材料在脱嵌锂过程的体积变化率、提高材料的电导率,也可以延长Si基材料的循环寿命。此外,Si合金的振实密度高、制备工艺简单,有利于规模化应用。在简要综述最近5年在Si基锂离子电池负极材料的纳米化和合金化方面的研究进展的同时,重点关注了不同纳米结构和合金化方法对其电化学储锂容量、倍率性能和循环稳定性能的影响。     

硅基锂离子电池负极材料的容量衰减及改进研究

硅材料的比容量(Li15Si4,3590mAh/g)是已商用化的石墨负极(LiC6,372mAh/g)的10倍,硅负极的商业化可有效提高单体电芯的容量,已成为当前研究热点。然而,由于硅负极材料在充放电循环时存在400%的体积膨胀,容易导致电极材料粉化开裂而从集流体上剥落,使得活性物质与活性物质、集流体之间失去电接触,同时不断形成新的固体电解质相界面膜(SEI膜),最终导致电化学性能的恶化。本研究从硅负极材料的储锂机理出发,提出硅负极材料锂化/脱锂化产生的体积膨胀效应导致的粉化开裂和SEI膜不稳定问题的最新调控方法和研究方向,为硅负极材料的研究应用提供支持。     

一种Si/NiSi2@C复合锂离子电池负极材料的高效制备及其电化学性能

以Si粉和Ni粉为主要原材料,通过对Si粉和Ni粉的球磨处理,结合柠檬酸碳源的高温热解,制备出一种碳包覆的Si/NiSi_2@C复合材料。采用多种技术手段研究了不同Ni添加量和原位碳的引入对复合材料结构形貌及其作为锂离子电池负极材料的电化学性能的影响。结果表明,Si粉和Ni粉在球磨过程中反应生成了NiSi_2合金相,弥散分布于复合材料中。柠檬酸高温裂解碳包覆于Si/NiSi_2复合颗粒表面,为复合材料构建了良好的导电网络。NiSi_2和高温裂解碳不仅增加材料的导电性,而且缓冲了脱嵌锂过程中Si的体积膨胀,有效地提高了材料的电化学性能。由于NiSi_2的电化学嵌锂活性低,随着Ni添加量的增加,材料的首次充放电容量降低,但材料的循环稳定性有所增加。其中当Ni的添加量为5wt%的Si/NiSi_2@C复合材料首次充放电容量分别为2754和2235mAh/g,首次库伦效率超过80%,经100次循环后的容量保持为1242mAh/g,显示出良好的电化学性能。     

锂离子电池硅基负极研究进展

硅由于具有超石墨10倍的高理论容量和相对适中的放电平台而备受关注,是最具潜力的下一代锂离子电池负极材料之一。然而,硅的本征电导率低,且在嵌锂的过程中有着巨大的体积变化(300%),会导致材料粉化,电极崩塌,失去电接触。此外,在电解液中硅表面的SEI膜重复形成也导致了极化增大,库伦效率降低和电解液消耗等问题。为了解决上述问题,实现硅电极的商业化应用,改善硅基电极的途径主要有:制备新型硅基材料抑制体积效应和提高电导率,改进粘结剂来加强电极结构防止电极崩塌,改进电解液以提高SEI膜质量和库伦效率。当前,改进硅基负极材料性能的主要策略是纳米化、孔隙化和复合化。粘结剂的改性也可分为开发新型粘结剂和修饰已有粘结剂。主要从硅基材料和粘结剂两方面论述了近年来的发展状况,并展望了其未来的发展方向。     

壳聚糖衍生碳包覆纳米硅复合材料锂离子电池性能研究

硅负极材料因具有较高的理论容量(Li₂₂Si₅合金相对应4 200 mAh/g)、较低的工作电压(0.2～0.3 V vs Li/Li⁺)和地球上丰富的原材料储备,成为代替石墨负极的理想材料之一。但是,低电导率及在循环过程中发生剧烈体积膨胀导致电极失效问题限制了硅负极材料的进一步发展。因此,本工作通过物理法利用壳聚糖和石墨对纳米硅实现碳包覆和复合,制备壳聚糖/石墨@纳米硅复合材料(C/G@Si复合材料),对C/G@Si复合材料的结构、形貌和电化学性能进行研究。结果表明：随着石墨添加量的提高,C/G@Si复合材料的可逆比容量略微下降,循环性能和导电性能显著提高。当添加50%(质量分数)石墨时,在100 mA/g的电流密度下,C/G@Si复合材料的首次放电比容量为1 136.1 mAh/g,循环充放电100次后剩余容量保持在658.5 mAh/g,展示出优异的电化学性能,对进一步推广硅碳负极材料具有一定的参考价值。     

碳热还原法制备Sn-C复合材料及其性能

用碳热还原法制备了Sn-C复合材料,通过XRD及SEM对其进行表征,并通过恒流充放电循环和慢速扫描循环伏安等方法对其电化学嵌脱锂性能做了研究.结果表明:SnO2碳热还原成金属Sn,晶粒尺寸约为42.8nm.该材料的首次嵌脱锂比容量分别可以达到1024.9和632.8mAh/g,循环15周以后的脱锂比容量为395.9mAh/g.     

Application and exploration of nanofibrous strategy in electrode design

The key to develop high specific energy rechargeable batteries is development of new electrode materials.The existing electrode materials still have many problems: the shuttle effect and poor conductivity of the sulfur cathode,the inevitable volume expansion of the silicon anode and the lithium dendrite of the lithium metal anode that cause short circuits,etc.Nanofibers,as active electrical materials,conductive additives and electrode bodies,can play multiple roles in electrode design.More interestingly,nanofibers can be functionalized to obtain better controllable properties (i.e.,electrolyte affinity,pore size distribution and surface electronic structure),thereby further enhancing electrochemical performance.In this article,the latest research progress in electrode design based on nanofibers is reviewed,including processing methods,structure,morphology and electrochemical performance.The key problems affecting the electrochemical performance of the electrode are also discussed,such as the preparation process,atomic structure,electrical conductivity,surface area and pore distribution of nanofibers,to provide reference points for nanofibers in excellent electrode design.     

源于溪木贼的高性能锂离子电池三维多孔生物质硅/碳复合负极材料

锂离子电池硅基负极材料的理论比容量比传统石墨材料高10倍,是最有前途的锂离子电池负极材料之一.然而硅基纳米材料的制备工艺复杂、成本高昂,严重限制了锂离子电池硅负极的商业应用.本工作采用溪木贼为原料,通过深度还原、浅度氧化和碳包覆工艺制备了三维多孔生物质硅/碳复合材料(多孔3D-bio-Si/C).三维多孔结构不仅有利于...     

无黏结剂柔性Si/CNT/纤维素复合阳极及其电化学性能

硅/碳复合材料作为最具潜力的下一代阳极材料,受到广泛关注。为减少硅巨大膨胀所产生的应力,避免硅纳米颗粒的粉化,提高硅基锂离子电池的电化学性能,制备了一种多微孔结构的多壁碳纳米管(MWCNTs)纸,嵌入纳米硅制得Si/MWCNTs/纤维素复合柔性锂离子电池阳极。FESEM显示,纳米硅均匀地嵌入在MWCNTs构建的三维导电网络中,纳米硅和导电载体具有良好的接触,使得界面电阻大幅下降,同时纳米硅在电池充放电过程中具有足够的膨胀空间,保证了材料的结构稳定性和化学稳定性。电化学检测显示,其首次放电比容量达到2024 mAh/g,循环30次后比容量维持在850 mAh/g,展示出良好的循环稳定性和较高的比容量。同时,其制作工艺相比传统涂敷类阳极得以简化,可操作性高,易于实现产业化。     

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.     

三维网络结构氧化铜纳米线锂离子电池负极材料的制备和性能研究

通过阳极氧化法和后退火处理在铜箔上合成了三维网络结构氧化铜纳米线,将其作为负极材料制备了无需添加粘结剂的锂离子电池。研究了恒压氧化时间对材料形貌和电化学性能的影响。在1C的倍率下,氧化1000 s制备的CuO纳米线表现出最高的1172 mAh/g首圈放电比容量和594 mAh/g的可逆比容量,500圈循环可逆比容量为607.6 mAh/g,可逆容量保留率为102.3%。交联的三维网络结构CuO纳米线相互支撑,提供稳定的结构,有效缓解了CuO纳米线作为锂离子电池负极材料中的体积膨胀问题,表现出了优异的倍率性能和循环寿命。     

锂离子电池硅基负极材料研究进展

硅基负极材料具有比容量大的优点,是高容量锂离子电池理想的负极材料。然而硅基材料在循环过程中容量衰减快,影响了其实用性。从硅复合物粉末和硅薄膜两个重要研究方面对硅基负极材料进行了综述,指出在Si基复合负极材料的研究中,单一途径改性提升循环性能的幅度有限,很难达到实用化阶段。硅的纳米化、无定形化、合金化及复合化等方法的综合运用成为硅基材料研究的主导方向。     

Synthesis and electrochemical characteristics of Sn-Sb-Ni alloy composite anode for Li-ion rechargeable batteries

Micro-scaled Sn-Sb-Ni alloy composite was synthesized from oxides of Sn, Sb and Ni via carbothermal reduction. The phase composition and electrochemical properties of the Sn-Sb-Ni alloy composite anode material were studied. The prepared alloy composite electrode exhibits a high specific capacity and a good cycling stability. The lithiation capacity was 530 mAh g⁻¹ in the first cycle and maintained at 370-380 mAh g⁻¹ in the following cycles. The good electrochemical performance may be attributed to its relatively large particle size and multi-phase characteristics. The former reason leads to the lower surface impurity and thus the lower initial capacity loss, while the latter results in a stepwise lithiation/delithiation behavior and a smooth volume change of electrode in cycles. The Sn-Sb-Ni alloy composite material shows a good candidate anode material for the rechargeable lithium ion batteries.     

2D Film of Carbon Nanofibers Elastically Astricted MnO Microparticles: A Flexible Binder‐Free Anode for Highly Reversible Lithium Ion Storage

MnO as anode materials has received particular interest owing to its high specific capacity, abundant resources, and low cost. However, serious problems related to the large volume change (>170%) during the lithiation/delithiation processes still results in poor rate capability and fast capacity decay. With homogenous crystals of MnO grown in the network of carbon nanofibers (CNF), binding effect of CNF can effectively weaken the volume change of MnO during cycles. In this work, a CNF/MnO flexible electrode for lithium‐ion batteries is designed and synthesized. The CNF play the roles of conductive channel and elastically astricting MnO particles during lithiation/delithiation. CNF/MnO as binder‐free anode delivers specific capacity of 983.8 mAh g^?1 after 100th cycle at a current density of 0.2 A g^?1, and 600 mAh g^?1 at 1 A g^?1 which are much better than those of pure MnO and pure CNF. The ex‐situ morphologies clearly show the relative volume change of MnO/CNF as anode under various discharging and charging times. CNF can elastically buffer the volume change of MnO during charging/discharging cycles. A facile and scalable approach for synthesizing a novel flexible binder‐free anode of CNF/MnO for potential application in highly reversible lithium storage devices is presented.     

25th Anniversary Article: Understanding the Lithiation of Silicon and Other Alloying Anodes for Lithium‐Ion Batteries

Alloying anodes such as silicon are promising electrode materials for next‐generation high energy density lithium‐ion batteries because of their ability to reversibly incorporate a high concentration of Li atoms. However, alloying anodes usually exhibit a short cycle life due to the extreme volumetric and structural changes that occur during lithium insertion/extraction; these transformations cause mechanical fracture and exacerbate side reactions. To solve these problems, there has recently been significant attention devoted to creating silicon nanostructures that can accommodate the lithiation‐induced strain and thus exhibit high Coulombic efficiency and long cycle life. In parallel, many experiments and simulations have been conducted in an effort to understand the details of volumetric expansion, fracture, mechanical stress evolution, and structural changes in silicon nanostructures. The fundamental materials knowledge gained from these studies has provided guidance for designing optimized Si electrode structures and has also shed light on the factors that control large‐volume change solid‐state reactions. In this paper, we review various fundamental studies that have been conducted to understand structural and volumetric changes, stress evolution, mechanical properties, and fracture behavior of nanostructured Si anodes for lithium‐ion batteries and compare the reaction process of Si to other novel anode materials.     

Nano‐Architectured Composite Anode Enabling Long‐Term Cycling Stability for High‐Capacity Lithium‐Ion Batteries

Failure mechanisms associated with silicon‐based anodes are limiting the implementation of high‐capacity lithium‐ion batteries. Understanding the aging mechanism that deteriorates the anode performance and introducing novel‐architectured composites offer new possibilities for improving the functionality of the electrodes. Here, the characterization of nano‐architectured composite anode composed of active amorphous silicon domains (a‐Si, 20 nm) and crystalline iron disilicide (c‐FeSi₂, 5–15 nm) alloyed particles dispersed in a graphite matrix is reported. This unique hierarchical architecture yields long‐term mechanical, structural, and cycling stability. Using advanced electron microscopy techniques, the nanoscale morphology and chemical evolution of the active particles upon lithiation/delithiation are investigated. Due to the volumetric variations of Si during lithiation/delithiation, the morphology of the a‐Si/c‐FeSi₂ alloy evolves from a core‐shell to a tree‐branch type structure, wherein the continuous network of the active a‐Si remains intact yielding capacity retention of 70% after 700 cycles. The root cause of electrode polarization, initial capacity fading, and electrode swelling is discussed and has profound implications for the development of stable lithium‐ion batteries.