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Register a new userLi$_x$CoO$_2$ phase stability studied by machine learning-enabled scale bridging between electronic structure, statistical mechanics and phase field theories
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Li$_xTM$O$_2$ (TM={Ni, Co, Mn}) are promising cathodes for Li-ion batteries, whose electrochemical cycling performance is strongly governed by crystal structure and phase stability as a function of Li content at the atomistic scale. Here, we use Li$_x$CoO$_2$ (LCO) as a model system to benchmark a scale-bridging framework that combines density functional theory (DFT) calculations at the atomistic scale with phase field modeling at the continuum scale to understand the impact of phase stability on microstructure evolution. This scale bridging is accomplished by incorporating traditional statistical mechanics methods with integrable deep neural networks, which allows formation energies for specific atomic configurations to be coarse-grained and incorporated in a neural network description of the free energy of the material. The resulting realistic free energy functions enable atomistically informed phase-field simulations. These computational results allow us to make connections to experimental work on LCO cathode degradation as a function of temperature, morphology and particle size.
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The ground states of Na$_x$CoO$_2$ ($0.0<x<1.0$) is studied by the LDA+Gutzwiller approach, where charge transfer and orbital fluctuations are all self-consistently treated {it ab-initio}. In contrast to previous studies, which are parameter-dependent, we characterized the phase diagram as: (1) Stoner magnetic metal for $x>0.6$ due to $a_{1g}$ van-Hove singularity near band top; (2) correlated non-magnetic metal without $e_g^{prime}$ pockets for $0.3<x<0.6$; (3) $e_g^{prime}$ pockets appear for $x<0.3$, and additional magnetic instability involves. Experimental quasi-particle properties is well explained, and the $a_{1g}$-$e_g^{prime}$ anti-crossing is attributed to spin-orbital coupling.
The idea that surface effects may play an important role in suppressing $e_g$ Fermi surface pockets on Na$_x$CoO$_2$ $(0.333 le x le 0.75)$ has been frequently proposed to explain the discrepancy between LDA calculations (performed on the bulk compound) which find $e_g$ hole pockets present and ARPES experiments, which do not observe the hole pockets. Since ARPES is a surface sensitive technique it is important to investigate the effects that surface formation will have on the electronic structure of Na$_{1/3}$CoO$_2$ in order to more accurately compare theory and experiment. We have calculated the band structure and Fermi surface of cleaved Na$_{1/3}$CoO$_2$ and determined that the surface non-trivially affects the fermiology in comparison to the bulk. Additionally, we examine the likelihood of possible hydroxyl cotamination and surface termination. Our results show that a combination of surface formation and contamination effects could resolve the ongoing controversy between ARPES experiments and theory.
Chemically exfoliated nanoscale few-layer thin Li$_x$CoO$_2$ samples are studied as function of annealing at various temperatures, using transmission electron microscopy (TEM) and Electron Energy Loss Spectroscopies (EELS), probing the O-K, Co-L$_{2,3}$ spectra along with low energy interband transitions. These spectra are compared with first-principles DFT calculations of -Im$[varepsilon^{-1}(q,omega)]$ and O-2p Partial Densities of States weighted by dipole matrix elements with the core wavefunction and including the O-1s core-hole and with known trends of the L$_2$/L$_3$ peak ratio to average Co valence. Trends in these spectra under the annealing procedures are established and correlated with the structural phase changes observed from diffraction TEM and High Resolution TEM images. The results are also correlated with conductivity measurements on samples subjected to the same annealing procedures. A gradual disordering of the Li and Co cations in the lattice is observed starting from a slight distortion of the pure LiCoO$_2$ $Rbar{3}m$ to $C2/m$ due to the lower Li content, followed by a $P2/m$ phase forming at 200$^o$C indicative of Li-vacancy ordering, formation of a spinel type $Fdbar{3}m$ phase around 250$^o$C and ultimately a rocksalt type $Fmbar{3}m$ phase above 350$^o$C. This disordering leads to a lowering of the band gap as established by low energy EELS. The O-K spectra of the rocksalt phase are only reproduced by a calculation for pure CoO and not for a model with random distribution of Li and Co. This indicates that there may be a loss of Li from the rocksalt regions of the sample at these higher temperatures. The conductivity measurements indicate a gradual drop in conductivity above 200$^o$C, which is clearly related to the more Li-Co interdiffused phases, in which a low-spin electronic structure is no longer valid and stronger correlation effects are expected.
Magnetic properties of Li$_x$CoO$_2$ for $x = 0.94, 0.75, 0.66$ and $0.51$ were investigated in frames of method combining Generalized Gradient Approximation with Dynamical Mean--Field Theory (GGA+DMFT). We found that a delicate interplay between Hunds exchange energy and $t_{2g}-e_g$ crystal field splitting is responsible for the high spin to low spin state transition for Co$^{4+}$ ions. The GGA+DMFT calculations show that at small doping level the Co$^{4+}$ ions adopt high spin state, while delithiation results in increase of the crystal field splitting and low spin state becomes preferable. The Co$^{3+}$ ions were found to stays in the low spin configuration for any $x$.
We have performed x-ray photoemission spectroscopy on the system of noncentrosymmetric superconductor, Li$_2$(Pd$_x$Pt$_{1-x}$3)B. For Li$_2$Pt$_3$B, we found 2 major peaks with 2 other weak components, and the band calculations were in agreement with the observation. The assignment of valence band features using the calculated partial density of states determined that Pt 5d and B 2p contribute to the density of states at the Fermi level. The effect of antisymmetric spin-orbit coupling on the band structure might have been probed, and the analysis on the effect of Pt incorporation into the system indicates the smooth evolution of electronic structures. We presented the measurements of core levels (Pd 3d, Pt 4f, and B 1s) and discussed the chemical bonding states and electronic structures from them.
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