Pristine Li-rich layered cathodes, such as Li(1.2)Ni(0.2)Mn(0.6)O(2) and Li(1.2)Ni(0.1)Mn(0.525)Co(0.175)O(2), were identified to exist in two different structures: LiMO(2)R3[overline]m and Li(2)MO(3)C2/m phases. Upon 300 cycles of charge/discharge, both phases gradually transform to the spinel structure. The transition from LiMO(2)R3[overline]m to spinel is accomplished through the migration of transition metal ions to the Li site without breaking down the lattice, leading to the formation of mosaic structured spinel grains within the parent particle. In contrast, transition from Li(2)MO(3)C2/m to spinel involves removal of Li(+) and O(2-), which produces large lattice strain and leads to the breakdown of the parent lattice. The newly formed spinel grains show random orientation within the same particle. Cracks and pores were also noticed within some layered nanoparticles after cycling, which is believed to be the consequence of the lattice breakdown and vacancy condensation upon removal of lithium ions. The AlF(3)-coating can partially relieve the spinel formation in the layered structure during cycling, resulting in a slower capacity decay. However, the AlF(3)-coating on the layered structure cannot ultimately stop the spinel formation. The observation of structure transition characteristics discussed in this paper provides direct explanation for the observed gradual capacity loss and poor rate performance of the layered composite. It also provides clues about how to improve the materials structure in order to improve electrochemical performance.
Although nanocrystal morphology is controllable using conventional colloidal synthesis, multiple characterization techniques are typically needed to determine key properties like the nucleation rate, induction time, growth rate, and the resulting morphology. Recently, researchers have demonstrated growth of nanocrystals by in situ electron beam reduction, offering direct observations of single nanocrystals and eliminating the need for multiple characterization techniques; however, they found nanocrystal morphologies consistent with two different growth mechanisms for the same electron beam parameters. Here we show that the electron beam current plays a role analogous to the concentration of reducing agent in conventional synthesis, by controlling the growth mechanism and final morphology of silver nanocrystals grown via in situ electron beam reduction. We demonstrate that low beam currents encourage reaction limited growth that yield nanocrystals with faceted structures, while higher beam currents encourage diffusion limited growth that yield spherical nanocrystals. By isolating these two growth regimes, we demonstrate a new level of control over nanocrystal morphology, regulated by the fundamental growth mechanism. We find that the induction threshold dose for nucleation is independent of the beam current, pixel dwell time, and magnification being used. Our results indicate that in situ electron microscopy data can be interpreted by classical models, by allowing simultaneous measurement of nucleation induction times, growth rates, and evolution of nanocrystal morphology. The results suggest that systematic dose experiments should be performed for all future in situ liquid studies to confirm the exact mechanisms underlying observations of nucleation and growth.
The Stardust spacecraft collected thousands of particles from comet 81P/Wild 2 and returned them to Earth for laboratory study. The preliminary examination of these samples shows that the nonvolatile portion of the comet is an unequilibrated assortment of materials that have both presolar and solar system origin. The comet contains an abundance of silicate grains that are much larger than predictions of interstellar grain models, and many of these are high-temperature minerals that appear to have formed in the inner regions of the solar nebula. Their presence in a comet proves that the formation of the solar system included mixing on the grandest scales.
this promising prospect is hindered by quite a few challenges in Li-S cells. The fi rst one is the intrinsically low electronic conductivity of sulfur (5 × 10 −30 S cm −1 ) and its end discharge products Li 2 S/Li 2 S 2 , which limits the full utilization of sulfur. [ 7 ] Accordingly, downsizing sulfur to nanosize particles and adding a large amount of carbon have been proposed to address the above issue. However, these methods unfortunately sacrifi ce the energy density of the Li-S cells. [ 2,6 ] In particular, high fractions of light carbon materials like porous carbon or carbon nanotube (CNT) do not contribute to the capacity at all but signifi cantly lower the volmetric energy density, which is undesired for higheffi cient portable devices or EV energy storage applications. [ 8 ] The second and more detrimental issue that limits Li-S cell performance is the formation of soluble long-chain polysulfi des such as Li 2 S 8 and Li 2 S 6 , which easily diffuse out of High energy and cost-effective lithium sulfur (Li-S) battery technology has been vigorously revisited in recent years due to the urgent need of advanced energy storage technologies for green transportation and large-scale energy storage applications. However, the market penetration of Li-S batteries has been plagued due to the gap in scientifi c knowledge between the fundamental research and the real application need. Here, a facile and effective approach to integrate commercial carbon nanoparticles into microsized secondary ones for application in high loading sulfur electrodes is proposed The slurry with the integrated particles is easily cast into electrode laminates with practically usable mass loadings. Uniform and crack-free coating with high loading of 2-8 mg cm −2 sulfur are successfully achieved. Based on the obtained thick electrodes, the dependence of areal specifi c capacity on mass loading, factors infl uencing electrode performance, and measures used to address the existing issues are studied and discussed.
Direct visualization of lead sulfide nanoparticle growth is demonstrated by selectively decomposing a chemical precursor from a multi-component solution using in situ liquid transmission electron microscopy. We demonstrate reproducible control over growth mechanisms that dictate the final morphology of nanostructures while observing growth in real-time with sub-nanometer spatial resolution. Furthermore, while an intense electron beam can initiate nanoparticle growth, it is also shown that a laser can trigger the reaction independently of the imaging electrons.
Magnesium batteries are an energy storage system that potentially offers high energy density, but development of new high voltage cathode materials and understanding of their electrochemical mechanism are critical to realize its benefits. Herein, we synthesize the layered MnO 2 polymorph (the birnessite phase) as a nanostructured phase supported on conductive carbon cloth and compare its electrochemistry and structural changes when it is cycled as a positive electrode material in a Mg-ion battery under nonaqueous or aqueous conditions. X-ray photoelectron spectroscopy and transmission electron microscopy studies show that a conversion mechanism takes place during cycling in a nonaqueous electrolyte, with the formation of MnOOH, MnO, and Mg(OH) 2 upon discharge. In aqueous cells, on the other hand, intercalation of Mg 2+ ions takes place, accompanied by expulsion of interlayer water and transformation to a spinel-like phase as evidenced by X-ray diffraction. Both systems are structurally quasireversible. The sharp contrast in behavior in the two electrolytes points to the important role of the desolvation energy of the Mg 2+ cation in nonaqueous systems.
Lithium (Li)- and manganese-rich (LMR) layered-structure materials are very promising cathodes for high energy density lithium-ion batteries. However, the voltage fading mechanism in these materials as well as its relationships to fundamental structural changes is far from being sufficiently understood. Here we report the detailed phase transformation pathway in the LMR cathode (Li[Li0.2Ni0.2Mn0.6]O2) during cycling for samples prepared by the hydrothermal assisted (HA) method. It is found that the transformation pathway of the LMR cathode is closely correlated to its initial structure and preparation conditions. The results reveal that the LMR cathode prepared by the HA approach experiences a phase transformation from the layered structure (initial C2/m phase transforms to R3̅m phase after activation) to a LT-LiCoO2 type defect spinel-like structure (with the Fd3̅m space group) and then to a disordered rock-salt structure (with the Fm3̅m space group). The voltage fade can be well correlated with Li ion insertion into octahedral sites, rather than tetrahedral sites, in both defect spinel-like and disordered rock-salt structures. The reversible Li insertion/removal into/from the disordered rock-salt structure is ascribed to the Li excess environment that permits Li percolation in the disordered rock-salt structure despite the increased kinetic barrier. Meanwhile, because of the presence of a large quantity of oxygen vacancies, a significant decrease in the Mn valence is detected in the cycled particle, which is below that anticipated for a potentially damaging Jahn–Teller distortion (+3.5). Clarification of the phase transformation pathway, cation redistribution, oxygen vacancy and Mn valence change provides unique understanding of the voltage fade and capacity degradation mechanisms in the LMR cathode. The results also inspire us to further enhance the reversibility of the LMR cathode via improved surface structural stability.
An operando electrochemical stage for the transmission electron microscope has been configured to form a "Li battery" that is used to quantify the electrochemical processes that occur at the anode during charge/discharge cycling. Of particular importance for these observations is the identification of an image contrast reversal that originates from solid Li being less dense than the surrounding liquid electrolyte and electrode surface. This contrast allows Li to be identified from Li-containing compounds that make up the solid-electrolyte interphase (SEI) layer. By correlating images showing the sequence of Li electrodeposition and the evolution of the SEI layer with simultaneously acquired and calibrated cyclic voltammograms, electrodeposition, and electrolyte breakdown processes can be quantified directly on the nanoscale. This approach opens up intriguing new possibilities to rapidly visualize and test the electrochemical performance of a wide range of electrode/electrolyte combinations for next generation battery systems.
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