Thermal treatments under a very wide range of oxygen pressures were used to probe the
composition and defect nature of a lithium-overstoichiometric “Li
x
0
CoO2” (x
0 > 1) sample
using X-ray powder diffraction, 7Li NMR, and electrochemical tests. It was found that at
900 °C, under atmospheric and elevated oxygen pressures, the lithium-overstoichiometric
sample gradually transformed to stoichiometric LiCoO2 by losing excess lithium in the form
of Li2O. In addition, it was shown that the defect associated with Co2+ and oxygen deficiency
as reported by Gorshkov et al. and Karelina et al. had a different NMR signature than that
present in Li-overstoichiometric samples. Therefore, it is believed that oxygen vacancies
are present but Co2+ ions are not present in Li
x
0
CoO2 (x
0 > 1). This leads to a formula
[Li]interslab[CoIII
1
-
3tCo3+(IS)
2tLit]slab[O2
-
t], involving an intermediate spin configuration for 2t
Co3+ ions in a square-based pyramidal site. This new model was supported by the NMR and
magnetic data of the lithium-overstoichiometric sample and its deintercalated compounds.
The effect of the defect on the end-of-discharge voltage profile during cycling was also
discussed.
In this work, exhaustive characterizations of 3D geometries of LiNi1/3Mn1/3Co1/3O2 (NMC), LiFePO4 (LFP), and NMC/LFP blended electrodes are undertaken for rational interpretation of their measured electrical properties and electrochemical performance. X‐ray tomography and focused ion beam in combination with scanning electron microscopy tomography are used for a multiscale analysis of electrodes 3D geometries. Their multiscale electrical properties are measured by using broadband dielectric spectroscopy. Finally, discharge rate performance are measured and analyzed by simple, yet efficient methods. It allows us to discriminate between electronic and ionic wirings as the performance limiting factors, depending on the discharge rate. This approach is a unique exhaustive analysis of the experimental relationships between the electrochemical behavior, the transport properties within the electrode, and its 3D geometry.
Abstract-This paper reports on the design and the evaluation of transmission control mechanisms specifically designed for multiplayer, distributed (serverless), interactive Internet applications. Distributed synchronization and dead reckoning are the main elements of this transmission control infrastructure. These mechanisms have been implemented in a fully distributed, multiplayer game application, i.e., one in which each entity in a game session computes its own local view of the session. The role of each entity is consequently to periodically send its own state to all other session participants (using RTP/UDP/IP multicast) and to periodically compute its own local view of the global game state using information received from the other participants. A detailed experimental analysis is provided using MBone and LAN experiments We investigate how the "quality" of the game is influenced by the frequency at which players exchange state information, as well as by network impairments such as packet loss and transmission delay.
This work is the first detailed study concerning the multiscale electronic transport and its temperature dependence in the LiNi1/3Co1/3Mn1/3O2 (NMC) family, high-capacity electrode materials for lithium ion batteries. Powders with two different mean cluster sizes (3 μm and 10 μm) but the same particle sizes (0.4 to 1.3 μm) were measured. The detailed formula of the studied compound is Li1.04Ni(2+)0.235Ni(3+)0.09Mn(4+)0.315Co(3+)0.32O2. Different electrical relaxations are evidenced, resulting from the polarizations at the different scales of the powder architecture. When the frequency increases, three dielectric relaxations are detected in the following order due to: (a) space-charge polarization (low-frequency range) owing to the interface between the sample and the conductive metallic layer deposited on it; (b) polarization of NMC clusters (micronic scale) induced by the existence of resistive junctions between them; and (c) polarization of NMC particles (at sub-micronic scale) induced by resistive junctions between them. High interatomic level conductivity of about 20 S m(-1) was evidenced and attributed to the contribution of the extended states and to a Brownian motion of the charge carriers with mean free path similar to the lattice constant. The ratio between sample and local conductivity is more than 10(5). The large conductivity drop of 3 to 4 orders of magnitude is observed from the particle to the cluster scale. A very large number of charge carriers are blocked by the interparticle junctions within the clusters. The conductivity drop from the cluster to the sample scale is comparatively very small, owing to the dense architecture of the NMC sample in which the spherical clusters are very piled up on each other.
The 3D morphology of LiNi1/3Mn1/3Co1/3O2 (NMC), LiFePO4 (LFP) and blended NMC/LFP electrodes envisioned for electric vehicles Li-ion batteries is characterized by both synchrotron X-ray tomography and FIB/SEM tomography. The size distribution of the active materials, the carbon phase and the pores, the specific surface area of the different solid phases, the concentration variations of the various phases through the total electrode thickness (X-ray tomography) or in smaller volumes (FIB/SEM tomography) are quantified. Results are assessed in relationship with the electrode composition and with their typical slurry rheological properties. Several heterogeneities are evidenced as the fingerprint of phenomena associated with the different processing steps of the electrodes.
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