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.
Lithium- and manganese-rich (LMR) layered-structure materials are very promising cathodes for high energy density lithium-ion batteries. However, their voltage fading mechanism and its relationships with fundamental structural changes are far from being well understood. Here we report for the first time the mitigation of voltage and energy fade of LMR cathodes by improving the atomic level spatial uniformity of the chemical species. The results reveal that LMR cathodes (Li[Li0.2Ni0.2M0.6]O2) prepared by coprecipitation and sol-gel methods, which are dominated by a LiMO2 type R3̅m structure, show significant nonuniform Ni distribution at particle surfaces. In contrast, the LMR cathode prepared by a hydrothermal assisted method is dominated by a Li2MO3 type C2/m structure with minimal Ni-rich surfaces. The samples with uniform atomic level spatial distribution demonstrate much better capacity retention and much smaller voltage fade as compared to those with significant nonuniform Ni distribution. The fundamental findings on the direct correlation between the atomic level spatial distribution of the chemical species and the functional stability of the materials may also guide the design of other energy storage materials with enhanced stabilities.
A variety of approaches are being made to enhance the performance of lithium ion batteries. Incorporating multivalence transition-metal ions into metal oxide cathodes has been identified as an essential approach to achieve the necessary high voltage and high capacity. However, the fundamental mechanism that limits their power rate and cycling stability remains unclear. The power rate strongly depends on the lithium ion drift speed in the cathode. Crystallographically, these transition-metal-based cathodes frequently have a layered structure. In the classic wisdom, it is accepted that lithium ion travels swiftly within the layers moving out/in of the cathode during the charge/discharge. Here, we report the unexpected discovery of a thermodynamically driven, yet kinetically controlled, surface modification in the widely explored lithium nickel manganese oxide cathode material, which may inhibit the battery charge/discharge rate. We found that during cathode synthesis and processing before electrochemical cycling in the cell nickel can preferentially move along the fast diffusion channels and selectively segregate at the surface facets terminated with a mix of anions and cations. This segregation essentially can lead to a higher lithium diffusion barrier near the surface region of the particle. Therefore, it appears that the transition-metal dopant may help to provide high capacity and/or high voltage but can be located in a "wrong" location that may slow down lithium diffusion, limiting battery performance. In this circumstance, limitations in the properties of lithium ion batteries using these cathode materials can be determined more by the materials synthesis issues than by the operation within the battery itself.
The kinetics of energy storage in transition metal oxides are usually limited by solid-state diffusion, and the strategy most often utilized to improve their rate capability is to reduce ion diffusion distances by utilizing nanostructured materials. Here, another strategy for improving the kinetics of layered transition metal oxides by the presence of structural water is proposed. To investigate this strategy, the electrochemical energy storage behavior of a model hydrated layered oxide, WO3·2H2O, is compared with that of anhydrous WO3 in an acidic electrolyte. It is found that the presence of structural water leads to a transition from battery-like behavior in the anhydrous WO3 to ideally pseudocapacitive behavior in WO3·2H2O. As a result, WO3·2H2O exhibits significantly improved capacity retention and energy efficiency for proton storage over WO3 at sweep rates as fast as 200 mV s–1, corresponding to charge/discharge times of just a few seconds. Importantly, the energy storage of WO3·2H2O at such rates is nearly 100% efficient, unlike in the case of anhydrous WO3. Pseudocapacitance in WO3·2H2O allows for high-mass loading electrodes (>3 mg cm–2) and high areal capacitances (>0.25 F cm–2 at 200 mV s–1) with simple slurry-cast electrodes. These results demonstrate a new approach for developing pseudocapacitance in layered transition metal oxides for high-power energy storage, as well as the importance of energy efficiency as a metric of performance of pseudocapacitive materials.
We studied Pt-Co bimetallic nanoparticles during oxidation in O2 and reduction in H2 atmospheres using an aberration corrected environmental transmission electron microscope. During oxidation Co migrates to the nanoparticle surface forming a strained epitaxial CoO film. It subsequently forms islands via strain relaxation. The atomic restructuring is captured as a function of time. During reduction cobalt migrates back to the bulk, leaving a monolayer of platinum on the surface.
Li-rich layered material Li1.2Ni0.2Mn0.6O2 possesses high voltage and high specific capacity, which makes it an attractive candidate for the transportation industry and sustainable energy storage systems. The rechargeable capacity of the Li-ion battery is linked largely to the structural stability of the cathode materials during the charge–discharge cycles. However, the structure and cation distribution in pristine Li1.2Ni0.2Mn0.6O2 have not yet been fully characterized. Using a combination of aberration-corrected scanning transmission electron microscopy, X-ray energy-dispersive spectroscopy (XEDS), electron energy loss spectroscopy (EELS), and complementary multislice image simulation, we have probed the crystal structure, cation/anion distribution, and electronic structure of the Li1.2Ni0.2Mn0.6O2 nanoparticle. The electronic structure and valence state of transition-metal ions show significant variations, which have been identified to be attributed to the oxygen deficiency near certain particle surfaces. Characterization of the nanoscale phase separation and cation ordering in the pristine material are critical for understanding the capacity and voltage fading of this material for battery application.
Surface modification of silicon nanoparticles via molecular layer deposition (MLD) has been recently proved to be an effective way for dramatically enhancing the cyclic performance in lithium ion batteries. However, the fundamental mechanism of how this thin layer of coating functions is not known, which is complicated by the inevitable presence of native oxide of several nanometers on the silicon nanoparticle. Using in situ TEM, we probed in detail the structural and chemical evolution of both uncoated and coated silicon particles upon cyclic lithiation/delithation. We discovered that upon initial lithiation, the native oxide layer converts to crystalline Li2O islands, which essentially increases the impedance on the particle, resulting in ineffective lithiation/delithiation and therefore low Coulombic efficiency. In contrast, the alucone MLD-coated particles show extremely fast, thorough, and highly reversible lithiation behaviors, which are clarified to be associated with the mechanical flexibility and fast Li(+)/e(-) conductivity of the alucone coating. Surprisingly, the alucone MLD coating process chemically changes the silicon surface, essentially removing the native oxide layer, and therefore mitigates side reactions and detrimental effects of the native oxide. This study provides a vivid picture of how the MLD coating works to enhance the Coulombic efficiency, preserves capacity, and clarifies the role of the native oxide on silicon nanoparticles during cyclic lithiation and delithiation. More broadly, this work also demonstrates that the effect of the subtle chemical modification of the surface during the coating process may be of equal importance to the coating layer itself.
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