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.     

A Uniform Self-Reinforced Organic/Inorganic Hybrid SEI Chelation Strategy on Microscale Silicon Surfaces for Stable-Cycling Anodes in Lithium-Ion Batteries

A promising anode material for Li-ion batteries, silicon (Si) suffers from volume expansion-induced pulverization and solid electrolyte interface (SEI) instability. Microscale Si with high tap density and high initial Coulombic efficiency (ICE) has become a more anticipated choice, but it will exacerbate the above issues. In this work, the polymer polyhedral oligomeric silsesquioxane-lithium bis (allylmalonato) borate (PSLB) is constructed by in situ chelation on microscale Si surfaces via click chemistry. This polymerized nanolayer has an “organic/inorganic hybrid flexible cross-linking” structure that can accommodate the volume change of Si. Under the stable framework formed by PSLB, a large number of oxide anions on the chain segment preferentially adsorb LiPF₆ and further induce the integration of inorganic-rich, dense SEI, which improves the mechanical stability of SEI and provides accelerated kinetics for Li⁺ transfer. Therefore, the Si4@PSLB anode exhibits significantly enhanced long-cycle performance. After 300 cycles at 1 A g⁻¹, it can still provide a specific capacity of 1083 mAh g⁻¹. Cathode-coupled with LiNi_0.9Co_0.05Mn_0.05O₂ (NCM90) in the full cell retains 80.8% of its capacity after 150 cycles at 0.5 C.     

Molecular-Cling-Effect of Fluoroethylene Carbonate Characterized via Ethoxy(pentafluoro)cyclotriphosphazene on SiOx/C Anode Materials – A New Perspective for Formerly Sub-Sufficient SEI Forming Additive Compounds

Effective electrolyte compositions are of primary importance in raising the performance of lithium-ion batteries (LIBs). Recently, fluorinated cyclic phosphazenes in combination with fluoroethylene carbonate (FEC) have been introduced as promising electrolyte additives, which can decompose to form an effective dense, uniform, and thin protective layer on the surface of electrodes. Although the basic electrochemical aspects of cyclic fluorinated phosphazenes combined with FEC were introduced, it is still unclear how these two compounds interact constructively during operation. This study investigates the complementary effect of FEC and ethoxy(pentafluoro)cyclotriphosphazene (EtPFPN) in aprotic organic electrolyte in LiNi_0.5Co_0.2Mn_0.3O ∥ SiO_x/C full cells. The formation mechanism of lithium ethyl methyl carbonate (LEMC)-EtPFPN interphasial intermediate products and the reaction mechanism of lithium alkoxide with EtPFPN are proposed and supported by Density Functional Theory calculations. A novel property of FEC is also discussed here, called molecular-cling-effect (MCE). To the best knowledge, the MCE has not been reported in the literature, although FEC belongs to one of the most investigated electrolyte additives. The beneficial MCE of FEC toward the sub-sufficient solid-electrolyte interphase forming additive compound EtPFPN is investigated via gas chromatography-mass spectrometry, gas chromatography high resolution-accurate mass spectrometry, in situ shell-isolated nanoparticle-enhanced Raman spectroscopy, and scanning electron microscopy.     

Dendrimer Based Binders Enable Stable Operation of Silicon Microparticle Anodes in Lithium-Ion Batteries

High-capacity anode materials (e.g., Si) are highly needed for high energy density battery systems, but they usually suffer from low initial coulombic efficiency (CE), short cycle life, and low-rate capability caused by large volume changes during the charge and discharge process. Here, a novel dendrimer-based binder for boosting the electrochemical performance of Si anodes is developed. The polyamidoamine (PMM) dendrimer not only can be used as binder, but also can be utilized as a crosslinker to construct 3D polyacrylic acid (PAA)-PMM composite binder for high-performance Si microparticles anodes. Benefiting from maximum interface interaction, strong average peeling force, and high elastic recovery rate of PAA-PMM composite, the Si electrode based on PAA-PMM achieves a high specific capacity of 3590 mAh g⁻¹ with an initial CE of 91.12%, long-term cycle stability with 69.80% retention over 200 cycles, and outstanding rate capability (1534.8 mAh g⁻¹ at 3000 mA g⁻¹). This work opens a new avenue to use dendrimer chemistry for the development of high-performance binders for high-capacity anode materials.     

Benchmarking the Effect of Particle Size on Silicon Anode Materials for Lithium-Ion Batteries (Small 42/2023)

High-capacity silicon has been regarded as one of the most promising anodes for high-energy lithium-ion batteries. However, it suffers from severe volume expansion, particle pulverization, and repeated solid electrolyte interphase (SEI) growth, which leads to rapid electrochemical failure, while the particle size also plays key role here and its effects remain elusive. In this paper, through multiple-physical, chemical, and synchrotron-based characterizations, the evolutions of the composition, structure, morphology, and surface chemistry of silicon anodes with the particle size ranging from 50 to 5 µm upon cycling are benchmarked, which greatly link to their electrochemical failure discrepancies. It is found that the nano- and micro-silicon anodes undergo similar crystal to amorphous phase transition, but quite different composition transition upon de-/lithiation; at the same time, the nano- and 1 µm-silicon samples present obviously different mechanochemical behaviors from the 5 µm-silicon sample, such as electrode crack, particle pulverization/crack as well as volume expansion; in addition, the micro-silicon samples possess much thinner SEI layer than the nano-silicon samples upon cycling, and also differences in SEI compositions. It is hoped this comprehensive study and understanding should offer critical insights into the exclusive and customized modification strategies to diverse silicon anodes ranging from nano to microscale.     

Nanostructured Silicon Anodes for Lithium Ion Rechargeable Batteries

Rechargeable lithium ion batteries are integral to today's information‐rich, mobile society. Currently they are one of the most popular types of battery used in portable electronics because of their high energy density and flexible design. Despite their increasing use at the present time, there is great continued commercial interest in developing new and improved electrode materials for lithium ion batteries that would lead to dramatically higher energy capacity and longer cycle life. Silicon is one of the most promising anode materials because it has the highest known theoretical charge capacity and is the second most abundant element on earth. However, silicon anodes have limited applications because of the huge volume change associated with the insertion and extraction of lithium. This causes cracking and pulverization of the anode, which leads to a loss of electrical contact and eventual fading of capacity. Nanostructured silicon anodes, as compared to the previously tested silicon film anodes, can help overcome the above issues. As arrays of silicon nanowires or nanorods, which help accommodate the volume changes, or as nanoscale compliant layers, which increase the stress resilience of silicon films, nanoengineered silicon anodes show potential to enable a new generation of lithium ion batteries with significantly higher reversible charge capacity and longer cycle life.     

Design Strategies to Enable the Efficient Use of Sodium Metal Anodes in High-Energy Batteries

Sodium-based batteries have attracted considerable attention and are recognized as ideal candidates for large-scale and low-cost energy storage. Sodium (Na) metal anodes are considered as one of the most promising anodes for next-generation, high-energy, Na-based batteries owing to their high theoretical specific capacity (1166 mA h g⁻¹) and low standard electrode potential. Herein, an overview of the recent developments in Na metal anodes for high-energy batteries is provided. The high reactivity and large volume expansion of Na metal anodes during charge and discharge make the electrode/electrolyte interphase unstable, leading to the formation of Na dendrites, short cycle life, and safety issues. Design strategies to enable the efficient use of Na metal anodes are elucidated, including liquid electrolyte engineering, electrode/electrolyte interface optimization, sophisticated electrode construction, and solid electrolyte engineering. Finally, the remaining challenges and future research directions are identified. It is hoped that this progress report will shape a consistent view of this field and provide inspiration for future research to improve Na metal anodes and enable the development of high-energy sodium batteries.     

Structure and Interface Engineering of Ultrahigh-Rate 3D Bismuth Anodes for Sodium-Ion Batteries

Sodium-ion batteries (SIBs) have attracted tremendous attention as promising low-cost energy storage devices in future grid-scale energy management applications. Bismuth is a promising anode for SIBs due to its high theoretical capacity (386 mAh g⁻¹). Nevertheless, the huge volume variation of Bi anode during (de)sodiation processes can cause the pulverization of Bi particulates and rupture of solid electrolyte interphase (SEI), resulting in quick capacity decay. It is demonstrated that rigid carbon framework and robust SEI are two essentials for stable Bi anodes. A lignin-derived carbonlayer wrapped tightly around the bismuth nanospheres provides a stable conductive pathway, while the delicate selection of linear and cyclic ether-based electrolytes enable robust and stable SEI films. These two merits enable the long-term cycling process of the LC-Bi anode. The LC-Bi composite delivers outstanding sodium-ion storage performance with an ultra-long cycle life of 10 000 cycles at a high current density of 5 A g⁻¹ and an excellent rate capability of 94% capacity retention at an ultrahigh current density of 100 A g⁻¹. Herein, the underlying origins of performance improvement of Bi anode are elucidated, which provides a rational design strategy for Bi anodes in practical SIBs.     

Ultrastable Potassium Storage Performance Realized by Highly Effective Solid Electrolyte Interphase Layer

Potassium ion‐batteries (PIBs) have attracted tremendous attention recently due to the abundance of potassium resources and the low standard electrode potential of potassium. Particularly, the solid‐electrolyte interphase (SEI) in the anode of PIBs plays a vital role in battery security and battery cycling performance due to the highly reactive potassium. However, the SEI in the anode for PIBs with traditional electrolytes is mainly composed of organic compositions, which are highly reactive with air and water, resulting in inferior cycle performance and safety hazards. Herein, a highly stable and effective inorganic SEI layer in the anode is formed with optimized electrolyte. As expected, the PIBs exhibit an ultralong cycle performance over 14 000 cycles at 2000 mA g^?1 and an ultrahigh average coulombic efficiency over 99.9%.     

薄膜厚度对α-SiOx薄膜负极电化学性能的影响

近年来, SiO_x作为锂离子电池负极, 由于其良好的循环稳定性、较大的容量以及对成分调控的可行性, 引起了广泛的关注。以往的许多研究都集中在阐明氧含量对SiO_x负极的影响, 尺寸效应对性能的影响规律很少被研究。此工作研究了不同厚度的薄膜型SiO_x负极材料的电化学性能。溅射制备SiO_x电极的Si/O比值为0.7、膜厚为450 nm时, 电极初始库仑效率(ICE)为71.68%、容量保持率92.01%。以上的最优性能主要归功于电荷转移电阻低、SEI层形成减少和循环过程中电极的结构稳定性。研究表明, 作为LIBs负极, 控制SiO_x负极的厚度可以有效改善电极材料的电化学性能。     

Carbon Nanotube-Reinforced Dual Carbon Stress-Buffering for Highly Stable Silicon Anode Material in Lithium-Ion Battery

Silicon (Si) anode suffers from huge volume expansion which causes poor structural stability in terms of electrode material, solid electrolyte interface, and electrode, limiting its practical application in high-energy-density lithium-ion batteries. Rationally designing architectures to optimize the stress distribution of Si/carbon (Si/C) composites has been proven to be effective in enhancing their structural stability and cycling stability, but this remains a big challenge. Here, metal-organic frameworks (ZIF-67)-derived carbon nanotube-reinforced carbon framework is employed as an outer protective layer to encapsulate the inner carbon-coated Si nanoparticles (Si@C@CNTs), which features dual carbon stress-buffering to enhance the structural stability of Si/C composite and prolong their cycling lifetime. Finite element simulation proves the structural advantage of dual carbon stress-buffering through significantly relieving stress concentration when Si lithiation. The outer carbon framework also accelerates the charge transfer efficiency during charging/discharging by the improvement of lithium-ion diffusion and electron transport. As a result, the Si@C@CNTs electrode exhibits excellent long-term lifetime and good rate capability, showing a specific capacity of 680 mAh g⁻¹ even at a high rate of 1 A g⁻¹ after 1000 cycles. This work provides insight into the design of robust architectures for Si/C composites by stress optimization.     

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.     

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.     

全固态薄膜锂充电电池的研究进展

全固态薄膜锂充电电池由于安全可靠性强、能量密度大、工作电压高、循环寿命长等诸多优点已经成为微型电子器件匹配电源的良好选择.阴极、阳极、固体电解质材料是全固态薄膜锂充电电池的重要组成部分,对于其开发和研究十分重要.综述了目前应用较多的阴极、阳极及固体电解质材料,并阐述了其物理特性、电化学性能和主要的制备方法;电池结构设计同样影响着整个电池的性能,介绍了电池结构对充放电特性的影响,且展望了其今后的研究热点和发展方向.