Smart surface coatings of silicon (Si) nanoparticles are shown to be good examples for dramatically improving the cyclability of lithium-ion batteries. Most coating materials, however, face significant challenges, including a low initial Coulombic efficiency, tedious processing, and safety assessment. In this study, a facile sol-gel strategy is demonstrated to synthesize commercial Si nanoparticles encapsulated by amorphous titanium oxide (TiO ), with core-shell structures, which show greatly superior electrochemical performance and high-safety lithium storage. The amorphous TiO shell (≈3 nm) shows elastic behavior during lithium discharging and charging processes, maintaining high structural integrity. Interestingly, it is found that the amorphous TiO shells offer superior buffering properties compared to crystalline TiO layers for unprecedented cycling stability. Moreover, accelerating rate calorimetry testing reveals that the TiO -encapsulated Si nanoparticles are safer than conventional carbon-coated Si-based anodes.
Silicon is one of the most promising anode materials for lithium‐ion batteries because of the highest known theoretical capacity and abundance in the earth' crust. Unfortunately, significant “breathing effect” during insertion/deinsertion of lithium in the continuous charge‐discharge processes causes the seriously structural degradation, thus losing specific capacity and increasing battery impedance. To overcome the resultant rapid capacity decay, significant achievements has been made in developing various nanostructures and surface coating approaches in terms of the improvement of structural stability and realizing the long cycle times. Here, the recent progress in surface and interface engineering of silicon‐based anode materials such as core‐shell, yolk‐shell, sandwiched structures and their applications in lithium‐ion batteries are reviewed. Some feasible strategies for the structural design and boosting the electrochemical performance are highlighted. Future research directions in the field of silicon‐based anode materials for next‐generation lithium‐ion batteries are summarized.
Carbon‐based materials have been considered as the most promising anode materials for both sodium‐ion batteries (SIBs) and potassium‐ion batteries (PIBs), owing to their good chemical stability, high electrical conductivity, and environmental benignity. However, due to the large sizes of sodium and potassium ions, it is a great challenge to realize a carbon anode with high reversible capacity, long cycle life, and high rate capability. Herein, by rational design, N‐doped 3D mesoporous carbon nanosheets (N‐CNS) are successfully synthesized, which can realize unprecedented electrochemical performance for both SIBs and PIBs. The N‐CNS possess an ultrathin nanosheet structure with hierarchical pores, ultrahigh level of pyridinic N/pyrrolic N, and an expanded interlayer distance. The beneficial features that can enhance the Na‐/K‐ion intercalation/deintercalation kinetic process, shorten the diffusion length for both ions and electrons, and accommodate the volume change are demonstrated. Hence, the N‐CNS‐based electrode delivers a high capacity of 239 mAh g−1 at 5 A g−1 after 10 000 cycles for SIBs and 321 mAh g−1 at 5 A g−1 after 5000 cycles for PIBs. First‐principles calculation shows that the ultrahigh doping level of pyridinic N/pyrrolic N contributes to the enhanced sodium and potassium storage performance by modulating the charge density distribution on the carbon surface.
Lithium-sulfur (Li-S) batteries have been regarded as the most promising candidates as the next-generation energy storage systems because of high theoretical capacities (Li: 3860 mAh g −1 and S: 1675 mAh g −1 ), low mass densities (Li: 0.534 g cm −3Lithium-sulfur (Li-S) batteries are strongly considered as next-generation energy storage systems because of their high energy density. However, the shuttling of lithium polysulfides (LiPS), sluggish reaction kinetics, and uncontrollable Li-dendrite growth severely degrade the electrochemical performance of Li-S batteries. Herein, a dual-functional flexible free-standing carbon nanofiber conductive framework in situ embedded with TiN-VN heterostructures (TiN-VN@CNFs) as an advanced host simultaneously for both the sulfur cathode (S/TiN-VN@CNFs) and the lithium anode (Li/TiN-VN@CNFs) is designed. As cathode host, the TiN-VN@CNFs can offer synergistic function of physical confinement, chemical anchoring, and superb electrocatalysis of LiPS redox reactions. Meanwhile, the well-designed host with excellent lithiophilic feature can realize homogeneous lithium deposition for suppressing dendrite growth. Combined with these merits, the full battery (denoted as S/TiN-VN@ CNFs || Li/TiN-VN@CNFs) exhibits remarkable electrochemical properties including high reversible capacity of 1110 mAh g −1 after 100 cycles at 0.2 C and ultralong cycle life over 600 cycles at 2 C. Even with a high sulfur loading of 5.6 mg cm −2 , the full cell can achieve a high areal capacity of 5.5 mAh cm −2 at 0.1 C. This work paves a new design from theoretical and experimental aspects for fabricating high-energy-density flexible Li-S full batteries.
Ordered mesoporous materials (OMMs) have received increasing interest due to their uniform pore size, high surface area, various compositions and wide applications in energy conversion and storage, biomedicine and environmental remediation, etc. The soft templating synthesis using surfactants or amphiphilic block copolymers is the most efficient method to produce OMMs with tailorable pore structure and surface property. However, due to the limited choice of commercially available soft templates, the common OMMs usually show small pore size and amorphous (or semicrystalline) frameworks. Tailor-made amphiphilic block copolymers with controllable molecular weights and compositions have recently emerged as alternative soft templates for synthesis of new OMMs with many unique features including adjustable mesostructures and framework compositions, ultralarge pores, thick pore walls, high thermal stability and crystalline frameworks. In this Perspective, recent progresses and some new insights into the coassembly process about the synthesis of OMMs based on these tailor-made copolymers as templates are summarized, and typical newly developed synthesis methods and strategies are discussed in depth, including solvent evaporation induced aggregation, ligand-assisted coassembly, solvent evaporation induced micelle fusion-aggregation assembly, homopolymer assisted pore expanding and carbon-supported crystallization strategy. Then, the applications of the obtained large-pore OMMs in catalysis, sensor, energy conversion and storage, and biomedicine by loading large-size guest molecules (e.g., protein and RNA), precious metal nanoparticles and quantum dots, are discussed. At last, the outlook on the prospects and challenges of future research about the synthesis of large-pore OMMs by using tailor-made amphiphilic block copolymers are included.
Core-shell magnetic mesoporous silica microspheres (Magn-MSMs) with tunable large mesopores in the shell are highly desired in biocatalysis, magnetic bioseparation, and enrichment. In this study, a shearing assisted interface coassembly in n-hexane/water biliquid systems is developed to synthesize uniform Magn-MSMs with magnetic core and mesoporous silica shell for an efficient size-selective biocatalysis. The synthesis features the rational control over the electrostatic interaction among cationic surfactant molecules, silicate oligomers, and Fe3O4@RF microspheres (RF: resorcinol formaldehyde) in the presence of shearing-regulated solubilization of n-hexane in surfactant micelles. Through this multicomponent interface coassembly, surfactant-silica mesostructured composite has been uniformly deposited on the Fe3O4@RF microspheres, and core-shell Magn-MSMs are obtained after removing the surfactant and n-hexane. The obtained Magn-MSMs possess excellent water dispersibility, uniform diameter (600 nm), large and tunable perpendicular mesopores (5.0-9.0 nm), high surface area (498-623 m(2)/g), large pore volume (0.91-0.98 cm(3)/g), and high magnetization (34.5-37.1 emu/g). By utilization of their large and open mesopores, Magn-MSMs with a pore size of about 9.0 nm have been demonstrated to be able to immobilize a large bioenzyme (trypsin with size of 4.0 nm) with a high loading capacity of ∼97 μg/mg via chemically binding. Magn-MSMs with immobilized trypsin exhibit an excellent convenient and size selective enzymolysis of low molecular proteins in the mixture of proteins of different sizes and a good recycling performance by using the magnetic separability of the microspheres.
A core-shell-shell heterostructure of Si nanoparticles as the core with mesoporous carbon and crystalline TiO as the double shells (Si@C@TiO) is utilized as an anode material for lithium-ion batteries, which could successfully tackle the vital setbacks of Si anode materials, in terms of intrinsic low conductivity, unstable solid-electrolyte interphase (SEI) films, and serious volume variations. Combined with the high theoretical capacity of the Si core (4200 mA h g), the double shells can perfectly avoid direct contact of Si with electrolyte, leading to stable SEI films and enhanced Coulombic efficiency. On the other hand, the carbon inner shell is effective at improving the overall conductivity of the Si-based electrode; the TiO outer shell is expected to serve as a rigid layer to achieve high structural stability and integrity of the core-shell-shell structure. As a result, the elaborate Si@C@TiO core-shell-shell nanoparticles are proven to show excellent Li storage properties. It delivers high reversible capacity of 1726 mA h g over 100 cycles, with outstanding cyclability of 1010 mA h g even after 710 cycles.
The application of high‐performance silicon‐based anodes, which are among the most prominent anode materials, is hampered by their poor conductivity and large volume expansion. Coupling of silicon‐based anodes with carbonaceous materials is a promising approach to address these issues. However, the distribution of carbon in reported hybrids is normally inhomogeneous and above the nanoscale, which leads to decay of coulombic efficiency during deep galvanostatic cycling. Herein, we report a porous silicon‐based nanocomposite anode derived from phenylene‐bridged mesoporous organosilicas (PBMOs) through a facile sol–gel method and subsequent pyrolysis. PBMOs show molecularly organic–inorganic hybrid character, and the resulting hybrid anode can inherit this unique structure, with carbon distributed homogeneously in the Si‐O‐Si framework at the atomic scale. This uniformly dispersed carbon network divides the silicon oxide matrix into numerous sub‐nanodomains with outstanding structural integrity and cycling stability.
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