RESUMEN
The Br- ion intercalated layered double hydroxide (LDH) of Li and Al obtained from the bayerite-Al(OH)3 precursor crystallizes in a structure different from that of the gibbsite-Al(OH)3 derived counterpart. Additionally, it undergoes temperature- and humidity-induced reversible interpolytype transformations. The dehydrated LDH (T ≈ 120 °C) adopts a structure of hexagonal symmetry (space group P3Ì 1m) and comprises a stacking of the metal hydroxide layers arranged one above another. On cooling and rehydration, the LDH adopts a structure of monoclinic symmetry with a stepwise increase in the stacking angle, ß. Using the structural synthon approach, based on the systematic elimination of the principal symmetry elements of the hexagonal crystal, structure models were generated for each of the two hydration steps (relative humidity â¼50%, >70%) and the structures refined (space group C2/m). The refined structures show that the interpolytype transitions are a result of rigid translations of successive metal hydroxide layers relative to one another by translation vectors (1/6, 0, 1) and (1/3, 0, 1), respectively.
RESUMEN
Layered double hydroxides are obtained by partial isomorphous substitution of divalent metal ions by trivalent metal ions in the structure of mineral brucite, Mg(OH)2. The widely reported three-layer polytype of rhombohedral symmetry, designated as polytype 3R1, is actually a one-layer polytype of monoclinic symmetry (space group C2/m, a = 5.401 Å, b = 9.355 Å, c = 11.02 Å, ß = 98.89°). This structure has a cation-ordered metal hydroxide layer defined by a supercell a = â3 × a0; b = 3 × a0 (a0 = cell parameter of the cation-disordered rhombohedral cell). Successive layers are translated by (1/3, 0, 1) relative to one another. When successive metal hydroxide layers are translated by (2/3, 0, 1) relative to one another, the resultant crystal, also of monoclinic symmetry, generates a powder pattern corresponding to the polytype hitherto designated as 3R2. This structure model not only removes all the anomalies intrinsic to the widely accepted cation-disordered structure but also abides by Pauling's rule that forbids trivalent cations from occupying neighboring sites and suggests that it is unnecessary to invoke rhombohedral symmetry when the metal hydroxide layer is cation ordered. These results have profound implications for the correct description of polytypism in this family of layered compounds.
RESUMEN
The high Li-ion conductivity and wide electrochemical stability of Li-rich garnets (Li7La3Zr2O12) make them one of the leading solid electrolyte candidates for solid-state batteries. Dopants such as Al and Ga are typically used to enable stabilization of the high Li+ ion-conductive cubic phase at room temperature. Although numerous studies exist that have characterized the electrochemical properties, structure, and lithium diffusion in Al- and Ga-LLZO, the local structure and site occupancy of dopants in these compounds are not well understood. Two broad 27Al or 69,71Ga resonances are often observed with chemical shifts consistent with tetrahedrally coordinated Al/Ga in the magic angle spinning nuclear magnetic resonance (MAS NMR) spectra of both Al- and Ga-LLZO, which have been assigned to either Al and/or Ga occupying 24d and 96h/48g sites in the LLZO lattice or the different Al/Ga configurations that arise from different arrangements of Li around these dopants. In this work, we unambiguously show that the side products γ-LiAlO2 and LiGaO2 lead to the high frequency resonances observed by NMR spectroscopy and that both Al and Ga only occupy the 24d site in the LLZO lattice. Furthermore, it was observed that the excess Li often used during synthesis leads to the formation of these side products by consuming the Al/Ga dopants. In addition, the consumption of Al/Ga dopants leads to the tetragonal phase formation commonly observed in the literature, even after careful mixing of precursors. The side-products can exist even after sintering, thereby controlling the Al/Ga content in the LLZO lattice and substantially influencing the lithium-ion conductivity in LLZO, as measured here by electrochemical impedance spectroscopy.
RESUMEN
Garnet solid-electrolyte-based Li-metal batteries can be used in energy storage devices with high energy densities and thermal stability. However, the tendency of garnets to form lithium hydroxide and carbonate on the surface in an ambient atmosphere poses significant processing challenges. In this work, the decomposition of surface layers under various gas environments is studied by using two surface-sensitive techniques, near-ambient-pressure X-ray photoelectron spectroscopy and grazing incidence X-ray diffraction. It is found that heating to 500 °C under an oxygen atmosphere (of 1 mbar and above) leads to a clean garnet surface, whereas low oxygen partial pressures (i.e., in argon or vacuum) lead to additional graphitic carbon deposits. The clean surface of garnets reacts directly with moisture and carbon dioxide below 400 and 500 °C, respectively. This suggests that additional CO2 concentration controls are needed for the handling of garnets. By heating under O2 along with avoiding H2O and CO2, symmetric cells with less than 10 Ωcm2 interface resistance are prepared without the use of any interlayers; plating currents of >1 mA cm-2 without dendrite initiation are demonstrated.
RESUMEN
Li- and Mn-rich layered oxides (Li1.2Ni0.2Mn0.6O2) are actively pursued as high energy and sustainable alternatives to the current Li-ion battery cathodes that contain Co. However, the severe decay in discharge voltage observed in these cathodes needs to be addressed before they can find commercial applications. A few mechanisms differing in origin have been proposed to explain the voltage fade, which may be caused by differences in material composition, morphology and electrochemical testing protocols. Here, these challenges are addressed by synthesising Li1.2Ni0.2Mn0.6O2 using three different hydrothermal and solid-state approaches and studying their degradation using the same cell design and cycling protocols. The voltage fade is found to be similar under the same electrochemical testing protocols, regardless of the synthesis method. X-ray absorption near edge, extended X-ray absorption fine structure spectroscopies, and energy loss spectroscopy in a scanning transmission electron microscope indicate only minor changes in the bulk Mn oxidation state but reveal a much more reduced particle surface upon extended cycling. No spinel phase is seen via the bulk structural characterisation methods of synchrotron X-ray diffraction, 7Li magic angle spinning solid state nuclear magnetic resonance and Raman spectroscopy. Thus, the voltage fade is believed to largely result from a heavily reduced particle surface. This hypothesis is further confirmed by galvanostatic intermittent titration technique analysis, which indicates that only very small shifts in equilibrium potential take place, in contrast to the overpotential which builds up after cycling. This suggests that a major source of the voltage decay is kinetic in origin, resulting from a heavily reduced particle surface with slow Li transport.
RESUMEN
Imbibition of LiNO3 into gibbsite results in the formation of a single phase layered double hydroxide of the composition LiAl2(OH)6(NO3)·1.2H2O. This phase undergoes reversible dehydration along with the compression of the basal spacing accompanied by the reorientation of the nitrate in the interlayer gallery. The hydrated phase is a solid solution of two lattices: (i) a hexagonal lattice defining the ordering of atoms within the metal hydroxide layer, and (ii) a lattice of orthorhombic symmetry defining the ordering of atoms within the interlayer. DFT calculations of the hydration behaviour show that there is no registry between the two sublattices. In the dehydrated phase, the nitrate ion is intercalated with its molecular plane parallel to the metal hydroxide layer and the crystal adopts a structure of hexagonal symmetry.