Free-Standing LiNi_0.5Mn_1.5O₄/Carbon Nanofiber Network Film as Lightweight and High-Power Cathode for Lithium Ion Batteries

Lightweight and high-power LiNi0.5Mn1.5O4/carbon nanofiber (CNF) network electrodes are developed as a high-voltage cathode for lithium ion batteries. The LiNi0.5Mn1.5O4/CNF network electrodes are free-standing and can be used as a cathode without using any binder, carbon black, or metal current collector, and hence the total weight of the electrode is highly reduced while keeping the same areal loading of active materials. Compared with conventional electrodes, the LiNi0.5Mn1.5O4/CNF network electrodes can yield up to 55% reduction in total weight and 2.2 times enhancement in the weight percentage of active material in the whole electrode. Moreover, the LiNi0.5Mn1.5O4/carbon nanofiber (CNF) network electrodes showed excellent current rate capability in the large-current test up to 20C (1C = 140 mAh/g), when the conventional electrodes showed almost no capacity at the same condition. Further analysis of polarization resistance confirmed the favorable conductivity from the CNF network compared with the conventional electrode structure. By reducing the weight, increasing the working voltage, and improving the large-current rate capability simultaneously, the LiNi0.5Mn1.5O4/CNF electrode structure can highly enhance the energy/power density of lithium ion batteries and thus holds great potential to be used with ultrathin, ultralight electronic devices as well as electric vehicles and hybrid electric vehicles

Porous Doped Silicon Nanowires for Lithium Ion Battery Anode with Long Cycle Life

Porous silicon nanowires have been well studied for various applications; however, there are only very limited reports on porous silicon nanowires used for energy storage. Here, we report both experimental and theoretical studies of porous doped silicon nanowires synthesized by direct etching of boron-doped silicon wafers. When using alginate as a binder, porous silicon nanowires exhibited superior electrochemical performance and long cycle life as anode material in a lithium ion battery. Even after 250 cycles, the capacity remains stable above 2000, 1600, and 1100 mAh/g at current rates of 2, 4, and 18 A/g, respectively, demonstrating high structure stability due to the high porosity and electron conductivity of the porous silicon nanowires. A mathematic model coupling the lithium ion diffusion and the strain induced by lithium intercalation was employed to study the effect of porosity and pore size on the structure stability. Simulation shows silicon with high porosity and large pore size help to stabilize the structure during charge/discharge cycles

Solution Ionic Strength Engineering As a Generic Strategy to Coat Graphene Oxide (GO) on Various Functional Particles and Its Application in High-Performance Lithium–Sulfur (Li–S) Batteries

A generic and facile method of coating graphene oxide (GO) on particles is reported, with sulfur/GO core–shell particles demonstrated as an example for lithium–sulfur (Li–S) battery application with superior performance. Particles of different diameters (ranging from 100 nm to 10 μm), geometries, and compositions (sulfur, silicon, and carbon) are successfully wrapped up by GO, by engineering the ionic strength in solutions. Importantly, our method does not involve any chemical reaction between GO and the wrapped particles, and therefore, it can be extended to vast kinds of functional particles. The applications of sulfur/GO core–shell particles as Li–S battery cathode materials are further investigated, and the results show that sulfur/GO exhibit significant improvements over bare sulfur particles without coating. Galvanic charge–discharge test using GO/sulfur particles shows a specific capacity of 800 mAh/g is retained after 1000 cycles at 1 A/g current rate if only the mass of sulfur is taken into calculation, and 400 mAh/g if the total mass of sulfur/GO is considered. Most importantly, the capacity decay over 1000 cycles is less than 0.02% per cycle. The coating method developed in this study is facile, robust, and versatile and is expected to have wide range of applications in improving the properties of particle materials

Accelerated Degradation in a Quasi-Single-Crystalline Layered Oxide Cathode for Lithium-Ion Batteries Caused by Residual Grain Boundaries

The rapidly growing demand of electrical vehicles (EVs) requires high-energy-density lithium-ion batteries (LIBs) with excellent cycling stability and safety performance. However, conventional polycrystalline high-Ni cathodes severely suffer from intrinsic chemomechanical degradation and fast capacity fade. The emerging single-crystallization strategy offers a promising pathway to improve the cathode’s chemomechanical stability; however, the single-crystallinity of the cathode is not always guaranteed, and residual grain boundaries (GBs) could persist in nonideal synthesis conditions, leading to the formation of “quasi-single-crystalline” (QSC) cathodes. So far, there has been a lack of understanding of the influence of these residual GBs on the electrochemical performance and structural stability. Herein, we investigate the degradation pathway of a QSC high-Ni cathode through transmission electron microscopy and X-ray techniques. The residual GBs caused by insufficient calcination time dramatically exacerbate the cathode’s chemomechanical instability and cycling performance. Our work offers important guidance for next-generation cathodes for long-life LIBs

Large-Scale Synthesis of SnO₂ Nanosheets with High Lithium Storage Capacity

Large-Scale Synthesis of SnO2 Nanosheets with High Lithium Storage Capacit

Large-Scale Fabrication, 3D Tomography, and Lithium-Ion Battery Application of Porous Silicon

Recently, silicon-based lithium-ion battery anodes have shown encouraging results, as they can offer high capacities and long cyclic lifetimes. The applications of this technology are largely impeded by the complicated and expensive approaches in producing Si with desired nanostructures. We report a cost-efficient method to produce nanoporous Si particles from metallurgical Si through ball-milling and inexpensive stain-etching. The porosity of porous Si is derived from particle’s three-dimensional reconstructions by scanning transmission electron microscopy (STEM) tomography, which shows the particles’ highly porous structure when etched under proper conditions. Nanoporous Si anodes with a reversible capacity of 2900 mAh/g was attained at a charging rate of 400 mA/g, and a stable capacity above 1100 mAh/g was retained for extended 600 cycles tested at 2000 mA/g. The synthetic route is low-cost and scalable for mass production, promising Si as a potential anode material for the next-generation lithium-ion batteries with enhanced capacity and energy density

Vapor Trapping Growth of Single-Crystalline Graphene Flowers: Synthesis, Morphology, and Electronic Properties

We report a vapor trapping method for the growth of large-grain, single-crystalline graphene flowers with grain size up to 100 μm. Controlled growth of graphene flowers with four lobes and six lobes has been achieved by varying the growth pressure and the methane to hydrogen ratio. Surprisingly, electron backscatter diffraction study revealed that the graphene morphology had little correlation with the crystalline orientation of underlying copper substrate. Field effect transistors were fabricated based on graphene flowers and the fitted device mobility could achieve ∼4200 cm² V^–1 s^–1 on Si/SiO₂ and ∼20 000 cm² V^–1s^–1 on hexagonal boron nitride (h-BN). Our vapor trapping method provides a viable way for large-grain single-crystalline graphene synthesis for potential high-performance graphene-based electronics

Step-Edge-Guided Nucleation and Growth of Aligned WSe₂ on Sapphire <i>via</i> a Layer-over-Layer Growth Mode

Two-dimensional (2D) materials beyond graphene have drawn a lot of attention recently. Among the large family of 2D materials, transitional metal dichalcogenides (TMDCs), for example, molybdenum disulfides (MoS₂) and tungsten diselenides (WSe₂), have been demonstrated to be good candidates for advanced electronics, optoelectronics, and other applications. Growth of large single-crystalline domains and continuous films of monolayer TMDCs has been achieved recently. Usually, these TMDC flakes nucleate randomly on substrates, and their orientation cannot be controlled. Nucleation control and orientation control are important steps in 2D material growth, because randomly nucleated and orientated flakes will form grain boundaries when adjacent flakes merge together, and the formation of grain boundaries may degrade mechanical and electrical properties of as-grown materials. The use of single crystalline substrates enables the alignment of as-grown TMDC flakes via a substrate–flake epitaxial interaction, as demonstrated recently. Here we report a step-edge-guided nucleation and growth approach for the aligned growth of 2D WSe₂ by a chemical vapor deposition method using C-plane sapphire as substrates. We found that at temperatures above 950 °C the growth is strongly guided by the atomic steps on the sapphire surface, which leads to the aligned growth of WSe₂ along the step edges on the sapphire substrate. In addition, such atomic steps facilitate a layer-over-layer overlapping process to form few-layer WSe₂ structures, which is different from the classical layer-by-layer mode for thin-film growth. This work introduces an efficient way to achieve oriented growth of 2D WSe₂ and adds fresh knowledge on the growth mechanism of WSe₂ and potentially other 2D materials

Chemomechanically Stable Ultrahigh-Ni Single-Crystalline Cathodes with Improved Oxygen Retention and Delayed Phase Degradations

The pressing demand in electrical vehicle (EV) markets for high-energy-density lithium-ion batteries (LIBs) requires further increasing the Ni content in high-Ni and low-Co cathodes. However, the commercialization of high-Ni cathodes is hindered by their intrinsic chemomechanical instabilities and fast capacity fade. The emerging single-crystalline strategy offers a promising solution, yet the operation and degradation mechanism of single-crystalline cathodes remain elusive, especially in the extremely challenging ultrahigh-Ni (Ni > 90%) regime whereby the phase transformation, oxygen loss, and mechanical instability are exacerbated with increased Ni content. Herein, we decipher the atomic-scale stabilization mechanism controlling the enhanced cycling performance of an ultrahigh-Ni single-crystalline cathode. We find that the charge/discharge inhomogeneity, the intergranular cracking, and oxygen-loss-related phase degradations that are prominent in ultrahigh-Ni polycrystalline cathodes are considerably suppressed in their single-crystalline counterparts, leading to improved chemomechanical and cycling stabilities of the single-crystalline cathodes. Our work offers important guidance for designing next-generation single-crystalline cathodes for high-capacity, long-life LIBs

Hierarchical Carbon-Coated Ball-Milled Silicon: Synthesis and Applications in Free-Standing Electrodes and High-Voltage Full Lithium-Ion Batteries

Lithium-ion batteries have been regarded as one of the most promising energy storage devices, and development of low-cost batteries with high energy density is highly desired so that the cost per watt-hour ($/Wh) can be minimized. In this work, we report using ball-milled low-cost silicon (Si) as the starting material and subsequent carbon coating to produce low-cost hierarchical carbon-coated (HCC) Si. The obtained particles prepared from different Si sources all show excellent cycling performance of over 1000 mAh/g after 1000 cycles. Interestingly, we observed <i>in situ</i> formation of porous Si, and it is well confined in the carbon shell based on postcycling characterization of the hierarchical carbon-coated metallurgical Si (HCC-M-Si) particles. In addition, lightweight and free-standing electrodes consisting of the HCC-M-Si particles and carbon nanofibers were fabricated, which achieved 1015 mAh/g after 100 cycles based on the total mass of the electrodes. Compared with conventional electrodes, the lightweight and free-standing electrodes significantly improve the energy density by 745%. Furthermore, LiCoO₂ and LiNi_0.5Mn_1.5O₄ cathodes were used to pair up with the HCC-M-Si anode to fabricate full cells. With LiNi_0.5Mn_1.5O₄ as cathode, an energy density up to 547 Wh/kg was achieved by the high-voltage full cell. After 100 cycles, the full cell with a LiNi_0.5Mn_1.5O₄ cathode delivers 46% more energy density than that of the full cell with a LiCoO₂ cathode. The systematic investigation on low-cost Si anodes together with their applications in lightweight free-standing electrodes and high-voltage full cells will shed light on the development of high-energy Si-based lithium-ion batteries for real applications