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.     

Chemical,Structural, and Electronic Aspects of Formation and Degradation Behavior on Different Length Scales of Ni‐Rich NCM and Li‐Rich HE‐NCM Cathode Materials in Li‐Ion Batteries

In order to satisfy the energy demands of the electromobility market, both Ni‐rich and Li‐rich layered oxides of NCM type are receiving much attention as high‐energy‐density cathode materials for application in Li‐ion batteries. However, due to different stability issues, their longevity is limited. During formation and continuous cycling, especially the electronic and crystal structure suffers from various changes, eventually leading to fatigue and mechanical degradation. In recent years, comprehensive battery research has been conducted at Karlsruhe Institute of Technology, mainly aiming at better understanding the primary degradation processes occurring in these layered transition metal oxides. The characteristic process of formation and mechanisms of fatigue are fundamentally characterized and the effect of chemical composition on cell chemistry, electrochemistry, and cycling stability is addressed on different length scales by use of state‐of‐the‐art analytical techniques, ranging from “standard” characterization tools to combinations of advanced in situ and operando methods. Here, the results are presented and discussed within a broader scientific context.     

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.     

Exploring Critical Factors Affecting Strain Distribution in 1D Silicon‐Based Nanostructures for Lithium‐Ion Battery Anodes

Despite the advantage of high capacity, the practical use of the silicon anode is still hindered by large volume expansion during the severe pulverization lithiation process, which results in electrical contact loss and rapid capacity fading. Here, a combined electrochemical and computational study on the factor for accommodating volume expansion of silicon‐based anodes is shown. 1D silicon‐based nanostructures with different internal spaces to explore the effect of spatial ratio of voids and their distribution degree inside the fibers on structural stability are designed. Notably, lotus‐root‐type silicon nanowires with locally distributed void spaces can improve capacity retention and structural integrity with minimum silicon pulverization during lithium insertion and extraction. The findings of this study indicate that the distribution of buffer spaces, electrochemical surface area, as well as Li diffusion property significantly influence cycle performance and rate capability of the battery, which can be extended to other silicon‐based anodes to overcome large volume expansion.     

Direct Visualization of the Reversible O2−/O− Redox Process in Li‐Rich Cathode Materials

Conventional cathodes of Li‐ion batteries mainly operate through an insertion–extraction process involving transition metal redox. These cathodes will not be able to meet the increasing requirements until lithium‐rich layered oxides emerge with beyond‐capacity performance. Nevertheless, in‐depth understanding of the evolution of crystal and excess capacity delivered by Li‐rich layered oxides is insufficient. Herein, various in situ technologies such as X‐ray diffraction and Raman spectroscopy are employed for a typical material Li_1.2Ni_0.2Mn_0.6O₂, directly visualizing O^?? O^? (peroxo oxygen dimers) bonding mostly along the c‐axis and demonstrating the reversible O^2?/O^? redox process. Additionally, the formation of the peroxo O? O bond is calculated via density functional theory, and the corresponding O? O bond length of ≈1.3 Å matches well with the in situ Raman results. These findings enrich the oxygen chemistry in layered oxides and open opportunities to design high‐performance positive electrodes for lithium‐ion batteries.     

Si and Ge‐Based Anode Materials for Li‐, Na‐, and K‐Ion Batteries: A Perspective from Structure to Electrochemical Mechanism

Silicon and germanium are among the most promising candidates as anodes for Li‐ion batteries, meanwhile their potential application in sodium‐ and potassium‐ion batteries is emerging. The access of their entire potential requires a comprehensive understanding of their electrochemical mechanism. This Review highlights the processes taking place during the alloying reaction of Si and Ge with the alkali ions. Several associated challenges, including the volumetric expansion, particle pulverization, and uncontrolled formation of solid electrolyte interphase layer must be surmounted and different strategies, such as nanostructures and electrode formulation, have been implemented. Additionally, a new approach based on the use of layered Si and Ge‐based Zintl phases is presented. The versatility of this new family permits the tuning of their physical and chemical properties for specific applications. For batteries in particular, the layered structure buffers the volume expansion and exhibits an enhanced electronic conductivity, allowing high power applications.     

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.     

FeP@C Nanotube Arrays Grown on Carbon Fabric as a Low Potential and Freestanding Anode for High‐Performance Li‐Ion Batteries

An anode of self‐supported FeP@C nanotube arrays on carbon fabric (CF) is successfully fabricated via a facile template‐based deposition and phosphorization route: first, well‐aligned FeOOH nanotube arrays are simply obtained via a solution deposition and in situ etching route with hydrothermally crystallized (Co,Ni)(CO₃)_0.5OH nanowire arrays as the template; subsequently, these uniform FeOOH nanotube arrays are transformed into robust carbon‐coated Fe₃O₄ (Fe₃O₄@C) nanotube arrays via glucose adsorption and annealing treatments; and finally FeP@C nanotube arrays on CF are achieved through the facile phosphorization of the oxide‐based arrays. As an anode for lithium‐ion batteries (LIBs), these FeP@C nanotube arrays exhibit superior rate capability (reversible capacities of 945, 871, 815, 762, 717, and 657 mA h g⁻¹ at 0.1, 0.2, 0.4, 0.8, 1.3, and 2.2 A g⁻¹, respectively, corresponding to area specific capacities of 1.73, 1.59, 1.49, 1.39, 1.31, 1.20 mA h cm⁻² at 0.18, 0.37, 0.732, 1.46, 2.38, and 4.03 mA cm⁻², respectively) and a stable long‐cycling performance (a high specific capacity of 718 mA h g⁻¹ after 670 cycles at 0.5 A g⁻¹, corresponding to an area capacity of 1.31 mA h cm⁻² at 0.92 mA cm⁻²).     

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。