Recent research has shown that certain Li-oxide garnets with high mechanical, thermal, chemical, and electrochemical stability are excellent fast Li-ion conductors. However, the detailed crystal chemistry of Li-oxide garnets is not well understood, nor is the relationship between crystal chemistry and conduction behavior. An investigation was undertaken to understand the crystal chemical and structural properties, as well as the stability relations, of Li(7)La(3)Zr(2)O(12) garnet, which is the best conducting Li-oxide garnet discovered to date. Two different sintering methods produced Li-oxide garnet but with slightly different compositions and different grain sizes. The first sintering method, involving ceramic crucibles in initial synthesis steps and later sealed Pt capsules, produced single crystals up to roughly 100 μm in size. Electron microprobe and laser ablation inductively coupled plasma mass spectrometry (ICP-MS) measurements show small amounts of Al in the garnet, probably originating from the crucibles. The crystal structure of this phase was determined using X-ray single-crystal diffraction every 100 K from 100 K up to 500 K. The crystals are cubic with space group Ia3̅d at all temperatures. The atomic displacement parameters and Li-site occupancies were measured. Li atoms could be located on at least two structural sites that are partially occupied, while other Li atoms in the structure appear to be delocalized. (27)Al NMR spectra show two main resonances that are interpreted as indicating that minor Al occurs on the two different Li sites. Li NMR spectra show a single narrow resonance at 1.2-1.3 ppm indicating fast Li-ion diffusion at room temperature. The chemical shift value indicates that the Li atoms spend most of their time at the tetrahedrally coordinated C (24d) site. The second synthesis method, using solely Pt crucibles during sintering, produced fine-grained Li(7)La(3)Zr(2)O(12) crystals. This material was studied by X-ray powder diffraction at different temperatures between 25 and 200 °C. This phase is tetragonal at room temperature and undergoes a phase transition to a cubic phase between 100 and 150 °C. Cubic "Li(7)La(3)Zr(2)O(12)" may be stabilized at ambient conditions relative to its slightly less conducting tetragonal modification via small amounts of Al(3+). Several crystal chemical properties appear to promote the high Li-ion conductivity in cubic Al-containing Li(7)La(3)Zr(2)O(12). They are (i) isotropic three-dimensional Li-diffusion pathways, (ii) closely spaced Li sites and Li delocalization that allow for easy and fast Li diffusion, and (iii) low occupancies at the Li sites, which may also be enhanced by the heterovalent substitution Al(3+) ⇔ 3Li.
Racemic perhydrotriphenylene (PHTP) forms a polar inclusion
compound with 1-(4-nitrophenyl)piperazine
(NPP) as a guest molecule. Homochiral stacks of PHTP molecules
surround polar chains of hydrogen-bonded NPP
molecules in a channel-type, honeycomb architecture.
The NPP chains are arranged in an all-parallel (rather
than
an antiparallel) fashion. Crystals of
[PHTP]5[NPP] show second harmonic generation for
incident light of wavelength
1064 nm, an electro-optical and a pyroelectric effect. The X-ray
diffraction pattern exhibits Bragg-like reflections,
interspersed with planes of diffuse scattering and weak satellite
reflections superimposed on these planes, features
which are indicative of extensive disorder. In spite of this, an
orthorhombic average structure model could be deduced
from the Bragg-like reflections (space group
Cmc21, a = 15.023(2),
b = 23.198(2), and c = 4.730(1) Å
(T = 100
K), wR
2 = 0.088, goodness of fit 1.38). A
qualitative interpretation of diffuse and satelite scattering is given.
Crystals
of [PHTP]5[NPP] are approximately hexagonal
prisms. If the tailor-made additive
1-(p-tolyl)piperazine (TP) is present
during crystallization, the habit changes to approximately hexagonal
plates and TP is incorporated in small amounts.
Crystals of the composition
[PHTP]5[NPP]0.93[TP]0.07
lose the ability of second harmonic generation. The
observation
of polar properties for a crystal structure whose polar building
blocks, the -NO2···HN- hydrogen-bonded NPP
chains,
are 14−15 Å apart and separated by PHTP hydrocarbon molecules is
surprising, but can be explained in terms of a
Markov chain model of crystal growth. The same simple model
accounts for the loss of polarity in the presence of
the tailor-made additive TP. The knowledge gained during the
present analysis provides a rational tool for the
engineering of polar properties of PHTP and similar channel-type
inclusion compounds.
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