Microsphere‐Like SiO2/MXene Hybrid Material Enabling High Performance Anode for Lithium Ion Batteries

To address the non‐negligible volume expansion and the inherent poor electronic conductivity of silica (SiO₂) material, microsphere‐like SiO₂/MXene hybrid material is designed and successfully synthesized through the combination of the Stöber method and spray drying. The SiO₂ nanoparticles are firmly anchored on the laminated MXene by the bonding effect, which boosts the structural stability during the long‐term cycling process. The MXene matrix not only possesses high elasticity to buffer the volume variation of SiO₂ nanoparticles, but also promotes the transfer of electrons and lithium ions. Moreover, the microsphere wrapped with ductile MXene film reduces the specific surface area, relieves the side reactions, and enhances the coulombic efficiency. Therefore, superior electrochemical performance including high reversible capacity, outstanding cycle stability, high coulombic efficiency, especially in the first cycle, excellent rate capability as well as high areal capacity are acquired for SiO₂/MXene microspheres anode.     

Strong Surface‐Bound Sulfur in Carbon Nanotube Bridged Hierarchical Mo2C‐Based MXene Nanosheets for Lithium–Sulfur Batteries

In this work, hydroxyl‐functionalized Mo₂C‐based MXene nanosheets are synthesized by facilely removing the Sn layer of Mo₂SnC. The hydroxyl‐functionalized surface of Mo₂C suppresses the shuttle effect of lithium polysulfides (LiPSs) through strong interaction between Mo atoms on the MXenes surface and LiPSs. Carbon nanotubes (CNTs) are further introduced into Mo₂C phase to enlarge the specific surface area of the composite, improve its electronic conductivity, and alleviate the volume change during discharging/charging. The strong surface‐bound sulfur in the hierarchical Mo₂C‐CNTs host can lead to a superior electrochemical performance in lithium–sulfur batteries. A large reversible capacity of ≈925 mAh g ^{? 1} is observed after 250 cycles at a current density of 0.1 C (1 C = 1675 mAh g^?1) with good rate capability. Notably, the electrodes with high loading amounts of sulfur can also deliver good electrochemical performances, i.e., initial reversible capacities of ≈1314 mAh g^?1 (2.4 mAh cm^?2), ≈1068 mAh g^?1 (3.7 mAh cm^?2), and ≈959 mAh g^?1 (5.3 mAh cm^?2) at various areal loading amounts of sulfur (1.8, 3.5, and 5.6 mg cm^?2) are also observed, respectively.     

Nb2CTx MXene Derived Polymorphic Nb2O5

Previously, heat treatment was the only feasible route for tuning the crystal phases of niobium pentoxide (Nb₂O₅). With the use of Nb₂CT_x MXene precursors, the first case of phase tuning of Nb₂O₅ in the low-temperature hydrothermal synthesis using sulfuric acid regulating agents is presented. By varying the amount of the agent, four pure-phase Nb₂O₅ crystals and mixed phases in-between are obtained. The required amount is found to be related to the H-covered surface energy calculated based on density functional theory. Overall, MXene-derived B-phase Nb₂O₅ is of particular interest due to its exceptionally high capacities as lithium-ion battery anodes, which are three times higher than the routine synthesized one. Oxygen vacancies induced by crystallographic shear would be responsible for the extraordinary performance. The proposed phase tuning strategy encourages the prudent synthesis of difficult-to-obtain crystal phases.     

Photo-Rechargeable Li-Ion Batteries using TiS2 Cathode

Photo-rechargeable (solar) battery can be considered as an energy harvesting cum storage system, where it can charge the conventional metal-ion battery using light instead of electricity, without having other parasitic reactions. Here a two-electrode lithium-ion solar battery with multifaceted TiS₂–TiO₂ hybrid sheets as cathode. The choice of TiS₂–TiO₂ electrode ensures the formation of a type II semiconductor heterostructure while the lateral heterostructure geometry ensures high mass/charge transfer and light interactions with the electrode. TiS₂ has a higher lithium binding energy (1.6 eV) than TiO₂ (1.03 eV), ensuring the possibilities of higher amount of Li-ion insertion to TiS₂ and hence the maximum recovery with the photocharging, as further confirmed by the experiments. Apart from the demonstration of solar solid-state batteries, the charging of lithium-ion full cell with light indicates the formation of lithium intercalated graphite compounds, ensuring the charging of the battery without any other parasitic reactions at the electrolyte or electrode-electrolyte interfaces. Possible mechanisms proposed here for the charging and discharging processes of solar batteries, based on the experimental and theoretical results, indicate the potential of such systems in the forthcoming era of renewable energies.     

锂离子电池正极材料的研究进展

介绍了不同正极材料的结构，电化学性能，研究现状，探讨了影响正极材料电化学性能的若干因素，比较了不同粉体合成方法的优缺点，说明了软化学法在锂离子电池正极材料制备中的优越性。     

An Ultra-Stable Electrode-Solid Electrolyte Composite for High-Performance All-Solid-State Li-Ion Batteries

The low ionic and electronic conductivity between current solid electrolytes and high-capacity anodes limits the long-term cycling performance of all-solid-state lithium-ion batteries (ASSLIBs). Herein, this work reports the fabrication of an ultra-stable electrode-solid electrolyte composite for high-performance ASSLIBs enabled by the homogeneous coverage of ultrathin Mg(BH₄)₂ layers on the surface of each MgH₂ nanoparticle that are uniformly distributed on graphene. The initial discharge process of Mg(BH₄)₂ layers results in uniform coverage of MgH₂ nanoparticle with both LiBH₄ as the solid electrolyte and Li₂B₆ with even higher Li ion conductivity than LiBH₄. Consequently, the Li ion conductivity of graphene-supported MgH₂ nanoparticles covered with ultrathin Mg(BH₄)₂ layers is two orders of magnitude higher than that without Mg(BH₄)₂ layers. Moreover, the thus-formed inactive Li₂B₆ with strong adsorption capability toward LiBH₄, acts as a stabilizing framework, which, coupled with the structural support role of graphene, alleviates the volume change of MgH₂ nanoparticles and facilitates the intimate contact between LiBH₄ and individual MgH₂ nanoparticles, leading to the formation of uniform stable interfaces with high ionic and electronic conductivity on each MgH₂ nanoparticles. Hence, an ultrahigh specific capacity of 800 mAh g⁻¹ is achieved for MgH₂ at 2 A g⁻¹ after 350 cycles.     

Anode materials from MoS2 and multilayered holey graphene for Li-ion batteries

Abstract

The ratio between the components determines the capacity of MoS₂/carbon materials in lithium-ion batteries (LIB). However, the structure of the carbon component and the synthesis conditions determine the amount of MoS₂ that can be efficiently used in each particular case. We study the influence of components ratio in MoS₂/multilayer holey graphene (HG) materials on the capacity in LIB. The synthesis was carried out by hot pressing of MoS₃ and HG mixtures at 600?°C and 100?bar. These synthesis conditions resulted in the decomposition of MoS₃ with the formation of MoS₂ nanocrystals. Optimal component distribution and better cycling performance, reaching 591 mAh g^?1 at a current density of 0.1?A g^?1 and 408 mAh g^?1 at 1?A g^?1, were found for MoS₂/HG containing 30?wt.% of MoS₂. An increase of the MoS₂ ratio led to a decrease of cycling stability and capacity of the material.     

Multi-Scale Design of Ultra-Broadband Microwave Metamaterial Absorber Based on Hollow Carbon/MXene/Mo2C Microtube

Developing various nanocomposite microwave absorbers is a crucial means to address the issue of electromagnetic pollution, but remains a challenge in satisfying broadband absorption at low thickness with dielectric loss materials. Herein, an ultra-broadband microwave metamaterial absorber (MMA) based on hollow carbon/MXene/Mo₂C (HCMM) is fabricated by a multi-scale design strategy. The microscopic 1D hierarchical microtube structure of HCMM contributes to break through the limit of thickness, exhibiting a strong reflection loss of -66.30 dB (99.99997 wave absorption) at the thinnest matching thickness of 1.0 mm. Meanwhile, the strongest reflection loss of -87.28 dB is reached at 1.4 mm, superior to most MXene-based and Mo₂C-based microwave absorbers. Then, the macroscopic 3D structural metasurface based on the HCMM is simulated, optimized, and finally manufactured. The as-prepared flexible HCMM-based MMA realizes an ultra-broadband effective absorption in the range of 3.7-40.0 GHz at a thickness of 5.0 mm, revealing its potential for practical application in the electromagnetic compatibility field.     

3D-Printed Silicone Substrates as Highly Deformable Electrodes for Stretchable Li-Ion Batteries

Stretchable energy storage devices receive a considerable attention at present due to their growing demand for powering wearable electronics. A vital component in stretchable energy storage devices is its electrode which should endure a large and repeated number of mechanical deformations during its prolonged use. It is crucial to develop a technology to fabricate highly deformable electrode in an easy and an economic manner. Here, the fabrication of stretchable electrode substrates using 3D-printing technology is reported. The ink for fabricating it contains a mixture of sacrificial sugar particles and polydimethylsiloxane resin which solidifies upon thermal curing. The printed stretchable substrate attains a porous structure after leaching the sugar particles in water. The resulting printed porous stretchable substrates are then utilized as electrodes for Li-ion batteries (LIBs) after loading them with electrode materials. The batteries with stretchable electrodes exhibit a decent electrochemical performance comparable to that of the conventional electrodes. The stretchable electrodes also exhibit a stable electrochemical performance under various mechanical deformations and even after several hundreds of stretch/release cycles. This work provides a feasible route for constructing LIBs with high stretchability and enhanced electrochemical performance thereby providing a platform for realizing stretchable batteries for next generation wearable electronics.     

One-Dimensional Covalent Organic Framework as High-Performance Cathode Materials for Lithium-Ion Batteries

Covalent organic frameworks (COFs) have emerged as a new class of cathode materials for energy storage in recent years. However, they are limited to two-dimensional (2D) or three-dimensional (3D) framework structures. Herein, this work reports designed synthesis of a redox-active one-dimensional (1D) COF and its composites with 1D carbon nanotubes (CNTs) via in situ growth. Used as cathode materials for Li-ion batteries, the 1D COF@CNT composites with unique dendritic core–shell structure can provide abundant and easily accessible redox-active sites, which contribute to improve diffusion rate of lithium ions and the corresponding specific capacity. This synergistic structural design enables excellent electrochemical performance of the cathodes, giving rise to 95% utilization of redox-active sites, high rate capability (81% capacity retention at 10 C), and long cycling stability (86% retention after 600 cycles at 5 C). As the first example to explore the application of 1D COFs in the field of energy storage, this study demonstrates the great potential of this novel type of linear crystalline porous polymers in battery technologies.     

锂离子电池C-Sn-金属复合负极材料的研究进展

综述了锂离子电池碳材料与锡基合金复合材料的发展现状,总结了C-Sn二元复合材料的主要种类,并分析了它们作为负极材料的电化学性能特点;同时阐述了C-Sn-金属三元复合材料的发展,这种复合材料结合了碳材料的循环稳定性和合金材料的高比容量的优势,是具有发展前景的新型锂离子电池负极材料。     

Diatom Frustules Decorated with Co Nanoparticles for the Advanced Anode of Li-Ion Batteries

Silica is regarded as a promising anode material for lithium-ion batteries (LIBs) because of its high theoretical capacity. However, large volume variation and poor electrical conductivity are limiting factors for the development of SiO₂ anode materials. To solve this problem, combining SiO₂ with a conductive phase and designing hollow porous structures are effective ways. In this work, The Co(II)-EDTA chelate on the surface of diatom biosilica (DBS) frustules and obtained DBS@C-Co composites decorated with Co nanoparticles by calcination without a reducing atmosphere is first precipitated. The unique three-dimensional structure of diatom frustules provides enough space for the volume change of silica during lithiation/delithiation. Co nanoparticles effectively improve the electrical conductivity and electrochemical activity of silica. Through the synergistic effect of the hollow porous structure, carbon layer and Co nanoparticles, the DBS@C-Co-60 composite delivers a high reversible capacity of >620 mAh g⁻¹ at 100 mA g⁻¹ after 270 cycles. This study provides a new method for the synthesis of metal/silica composites and an opportunity for the development of natural resources as advanced active materials for LIBs.     

Chevrel Phase Mo6S8 Nanosheets Featuring Reversible Electrochemical Li-Ion Intercalation as Effective Dynamic-Phase Promoter for Advanced Lithium-Sulfur Batteries

Modifying sulfur cathodes with lithium polysulfides (LiPSs) adsorptive and electrocatalytic host materials is regarded as one of the most effective approaches to address the challenging problems in lithium-sulfur (Li-S) batteries. However, because of the high operating voltage window of Li–S batteries from 1.7 to 2.8 V, most of the host materials cannot participate in the sulfur redox reactions within the same potential region, which exhibit fixed or single functional property, hardly fulfilling the requirement of the complex and multiphase process. Herein, Chevrel phase Mo₆S₈ nanosheets with high electronic conductivity, fast ion transport capability, and strong polysulfide affinity are introduced to sulfur cathode. Unlike most previous inactive hosts with a fixed affinity or catalytic ability toward LiPSs, the reaction involving Mo₆S₈ is intercalative and the adsorbability for LiPSs as well as the ionic conductivity can be dynamically enhanced via reversible electrochemical lithiation of Mo₆S₈ to Li-ion intercalated Li_xMo₆S₈, thereby suppressing the shuttling effect and accelerating the conversion kinetics. Consequently, the Mo₆S₈ nanosheets act as an effective dynamic-phase promoter in Li–S batteries and exhibit superior cycling stability, high-rate capability, and low-temperature performance. This study opens a new avenue for the development of advanced hosts with dynamic regulation activity for high performance Li-S batteries.     

Co3O4 Nanosheets as Active Material for Hybrid Zn Batteries

The rapid development of electric vehicles and modern personal electronic devices is severely hindered by the limited energy and power density of the existing power sources. Here a novel hybrid Zn battery is reported which is composed of a nanostructured transition metal oxide‐based positive electrode (i.e., Co₃O₄ nanosheets grown on carbon cloth) and a Zn foil negative electrode in an aqueous alkaline electrolyte. The hybrid battery configuration successfully combines the unique advantages of a Zn–Co₃O₄ battery and a Zn–air battery, achieving a high voltage of 1.85 V in the Zn–Co₃O₄ battery region and a high capacity of 792 mAh g_Zn^?1. In addition, the battery shows high stability while maintaining high energy efficiency (higher than 70%) for over 200 cycles and high rate capabilities. Furthermore, the high flexibility of the carbon cloth substrate allows the construction of a flexible battery with a gel electrolyte, demonstrating not only good rechargeability and stability, but also reasonable mechanical deformation without noticeable degradation in performance. This work also provides an inspiring example for further explorations of high‐performance hybrid and flexible battery systems.     

Niobium-Carbide MXene Modified Hybrid Hole Transport Layer Enabling High-Performance Organic Solar Cells Over 19%

Niobium-carbide (Nb₂C) MXene as a new 2D material has shown great potential for application in photovoltaics due to its excellent electrical conductivity, large surface area, and superior transmittance. In this work, a novel solution-processable poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS)-Nb₂C hybrid hole transport layer (HTL) is developed to enhance the device performance of organic solar cells (OSCs). By optimizing the doping ratio of Nb₂C MXene in PEDOT:PSS, the best power convention efficiency (PCE) of 19.33% can be achieved for OSCs based on the ternary active layer of PM6:BTP-eC9:L8-BO, which is so far the highest value among those of single junction OSCs using 2D materials. It is found that the addition of Nb₂C MXene can facilitate the phase separation of the PEDOT and PSS segments, thus improving the conductivity and work function of PEDOT:PSS. The significantly enhanced device performance can be attributed to the higher hole mobility and charge extraction capability, as well as lower interface recombination probabilities generated by the hybrid HTL. Additionally, the versatility of the hybrid HTL to improve the performance of OSCs based on different nonfullerene acceptors is demonstrated. These results indicate the promising potential of Nb₂C MXene in the development of high-performance OSCs.     

Lamellarly Stacking Porous N,P Co‐Doped Mo2C/C Nanosheets as High Performance Anode for Lithium‐Ion Batteries

Layered stacking and highly porous N, P co‐doped Mo₂C/C nanosheets are prepared from a stable Mo‐enhanced hydrogel. The hydrogel is formed through the ultrafast cross‐linking of phosphomolybdic acid and chitosan. During the reduction of the composite hydrogel framework under inert gas protection, highly porous N and P co‐doped carbon nanosheets are produced with the in situ formation of ultrafine Mo₂C nanoparticles highly distributed throughout the nanosheets which are entangled via a hierarchical lamellar infrastructure. This unique architecture of the N, P co‐doped Mo₂C/C nanosheets tremendously promote the electrochemical activity and operate stability with high specific capacity and extremely stable cycling. In particular, this versatile synthetic strategy can also be extended to other polyoxometalate (such as phosphotungstic acid) to provide greater opportunities for the controlled fabrication of novel hierarchical nanostructures for next‐generation high performance energy storage applications.     

Porous Mo3P/Mo Nanorods as Efficient Mott-Schottky Cathode Catalysts for Low Polarization Li-CO2 Battery

Li-CO₂ battery with high energy density has aroused great interest recently, large-scale applications are hindered by the limited cathode catalysis performance and execrably cycle performance. Herein, Mo₃P/Mo Mott-Schottky heterojunction nanorod electrocatalyst with abundant porous structure is fabricated and served as cathodes for Li-CO₂ batteries. The Mo₃P/Mo cathodes exhibit ultra-high discharge specific capacity of 10 577 mAh g⁻¹, low polarization voltage of 0.15 V, and high energy efficiency of up to 94.7%. Mott-Schottky heterojunction formed by Mo and Mo₃P drives electron transfer and optimizes the surface electronic structure, which is beneficial to accelerate the interface reaction kinetics. Distinctively, during the discharge process, the C₂O₄²⁻ intermediates combine with Mo atoms to form a stable Mo-O coupling bridge on the catalyst surface, which effectively facilitate the formation and stabilization of Li₂C₂O₄ products. In addition, the construction of the Mo-O coupling bridge between the Mott-Schottky heterojunction and Li₂C₂O₄ promotes the reversible formation and decomposition of discharge products and optimizes the polarization performance of the Li-CO₂ battery. This work provides another pathway for the development of heterostructure engineering electrocatalysts for high-performance Li-CO₂ batteries.     

MnCO3 Cuboids from Spent LIBs: A New Age Displacement Anode to Build High-Performance Li-Ion Capacitors

The advantage of hybridizing battery and supercapacitor electrodes has succeeded recently in designing hybrid charge storage systems such as lithium-ion capacitors (LICs) with the benefits of higher energy than supercapacitors and more power density than batteries. However, sluggish Li-ion diffusion of battery anode is one of the main barriers and hampers the development of high-performance LICs. Herein, is introduced a new conversion/displacement type anode, MnCO₃, via effectively recycling spent Li-ion batteries cathodes for LICs applications. The MnCO₃ cuboids are regenerated from the spent LiMn₂O₄ cathodes by organic acid lixiviation process, and hydrothermal treatment displays excellent reversibility of 535  mAh g⁻¹ after 50  cycles with a Coulombic efficiency of >99%. Later, LIC is assembled with the regenerated MnCO₃ cubes in pre-lithiated form (Mn⁰ + Li₂CO₃) as anode and commercial activated carbon (AC) as the cathode, delivering a maximum energy density of 169.4 Wh kg⁻¹ at 25 °C with ultra-long durability of 15,000 cycles. Even at various atmospheres like −5 and 50 °C, this LIC can offer a energy densities of 53.8 and 119.5 Wh kg⁻¹, respectively. Remarkably, the constructed AC/Mn⁰ + Li₂CO₃-based LIC exhibits a good cycling performance for a continuous 1000 cycles with >91% retention invariably for all temperature conditions.     

Recent Advances in Layered Ti3C2Tx MXene for Electrochemical Energy Storage

Ti₃C₂T_x, a typical representative among the emerging family of 2D layered transition metal carbides and/or nitrides referred to as MXenes, has exhibited multiple advantages including metallic conductivity, a plastic layer structure, small band gaps, and the hydrophilic nature of its functionalized surface. As a result, this 2D material is intensively investigated for application in the energy storage field. The composition, morphology and texture, surface chemistry, and structural configuration of Ti₃C₂T_x directly influence its electrochemical performance, e.g., the use of a well‐designed 2D Ti₃C₂T_x as a rechargeable battery anode has significantly enhanced battery performance by providing more chemically active interfaces, shortened ion‐diffusion lengths, and improved in‐plane carrier/charge‐transport kinetics. Some recent progresses of Ti₃C₂T_x MXene are achieved in energy storage. This Review summarizes recent advances in the synthesis and electrochemical energy storage applications of Ti₃C₂T_x MXene including supercapacitors, lithium‐ion batteries, sodium‐ion batteries, and lithium–sulfur batteries. The current opportunities and future challenges of Ti₃C₂T_x MXene are addressed for energy‐storage devices. This Review seeks to provide a rational and in‐depth understanding of the relation between the electrochemical performance and the nanostructural/chemical composition of Ti₃C₂T_x, which will promote the further development of 2D MXenes in energy‐storage applications.     

锂离子电池正极材料LiCo1/3Ni1/3Mn1/3O2的研究进展

综述了近几年锂离子电池正极材料层状三元过渡金属氧化物LiCoxNiyMn1-x-yO2的研究进展，重点讨论了综合性能优异的LiCo1/3Ni1/3Mn1/3O2的电化学性能、结构、制备方法以及存在的不足，LiCo1/3Ni1/3Mn1/3O2与其它商业化正极材料相比具有高容量、热稳定性好、高倍率放电等诸多优异的性能，若能解决循环、存放等问题，将有望成为新一代锂离子电池正极材料。