Li7La3Zr2O12 (LLZO) is a promising electrolyte material for all-solid-state battery due to its high ionic conductivity and good stability with metallic lithium. In this article, we studied the effect of crucibles on the ionic conductivity and air stability by synthesizing 0.25Al doped LLZO pellets in Pt crucibles and alumina crucibles, respectively. The results show that the composition and microstructure of the pellets play important roles influencing the ionic conductivity, relative density, and air stability. Specifically, the 0.25Al-LLZO pellets sintered in Pt crucibles exhibit a high relative density (∼96%) and high ionic conductivity (4.48 × 10(-4) S cm(-1)). The ionic conductivity maintains 3.6 × 10(-4) S cm(-1) after 3-month air exposure. In contrast, the ionic conductivity of the pellets from alumina crucibles is about 1.81 × 10(-4) S cm(-1) and drops to 2.39 × 10(-5) S cm(-1) 3 months later. The large grains and the reduced grain boundaries in the pellets sintered in Pt crucibles are favorable to obtain high ionic conductivity and good air stability. X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy results suggest that the formation of Li2CO3 on the pellet surface is probably another main reason, which is also closely related to the relative density and the amount of grain boundary within the pellets. This work stresses the importance of synthesis parameters, crucibles included, to obtain the LLZO electrolyte with high ionic conductivity and good air stability.

Li 7 La 3 Zr 2 O 12 (LLZO) has been reported to react in humid air to form Li 2 CO 3 on the surface, which decreases ionic conductivity. To study the reaction mechanism, 0.5-mol Ta-doped LLZO (0.5Ta-LLZO) pellets are exposed in dry (humiditỹ 5%) and humid air (humidity~80%) for 6 weeks, respectively. After exposure in humid air, the formation of Li 2 CO 3 on the pellet surface is confirmed experimentally and the room-temperature ionic conductivity is found to drop from 6.45910 À4 S cm À1 to 3.61910 À4 S cm À1 . Whereas for the 0.5Ta-LLZO samples exposed in dry air, the amount of formed Li 2 CO 3 is much less and the ionic conductivity barely decreases. To further clarify the reaction mechanism of 0.5Ta-LLZO pellets with moisture, we decouple the reactions between 0.5Ta-LLZO with water and CO 2 by immersing 0.5Ta-LLZO pellets in deionized water for 1 week and then exposing them to ambient air for another week. After immersion in deionized water, Li + /H + exchange occurs and LiOH H 2 O forms on the surface, which is a necessary intermediate step for the Li 2 CO 3 formation. Based on these observations, a reaction model is proposed and discussed. K E Y W O R D Sgarnets, impedance spectroscopy, ion exchange, lithium oxide, Raman spectroscopy

The biogeographical relationships between far-separated populations, in particular, those in the mainland and islands, remain unclear for widespread species in eastern Asia where the current distribution of plants was greatly influenced by the Quaternary climate. Deciduous Oriental oak (Quercus variabilis) is one of the most widely distributed species in eastern Asia. In this study, leaf material of 528 Q. variabilis trees from 50 populations across the whole distribution (Mainland China, Korea Peninsular as well as Japan, Zhoushan and Taiwan Islands) was collected, and three cpDNA intergenic spacer fragments were sequenced using universal primers. A total of 26 haplotypes were detected, and it showed a weak phylogeographical structure in eastern Asia populations at species level, however, in the central-eastern region of Mainland China, the populations had more haplotypes than those in other regions, with a significant phylogeographical structure (N ST = 0.751> G ST = 0.690, P<0.05). Q. variabilis displayed high interpopulation and low intrapopulation genetic diversity across the distribution range. Both unimodal mismatch distribution and significant negative Fu’s FS indicated a demographic expansion of Q. variabilis populations in East Asia. A fossil calibrated phylogenetic tree showed a rapid speciation during Pleistocene, with a population augment occurred in Middle Pleistocene. Both diversity patterns and ecological niche modelling indicated there could be multiple glacial refugia and possible bottleneck or founder effects occurred in the southern Japan. We dated major spatial expansion of Q. variabilis population in eastern Asia to the last glacial cycle(s), a period with sea-level fluctuations and land bridges in East China Sea as possible dispersal corridors. This study showed that geographical heterogeneity combined with climate and sea-level changes have shaped the genetic structure of this wide-ranging tree species in East Asia.

Effects of drought stresses induced by polyethylene glycol (PEG) (0.0%, 10%, 15%, 20%, 25%, and 30%, with four replicates) on germination of Mongolian pine (Pinus sylvestris var. mongolica) seeds produced in plantations (southern Keerqin sandy land) and natural forests (Hulunbeier sandy plain) were observed. The results indicated that the seeds from both provenances did not germinate when PEG concentration was more than 25%. The time of initial germination and that of its completion of stressed seeds from both provenances were delayed when compared with the unstressed seeds. The germination capacity and germination rate of natural seeds were significantly higher than those of plantation seeds for all treatment levels (P < 0.05). The mean growth rates of radicle and hypocotyl from natural seeds were significantly higher than those from plantation seeds at all treatment levels below 20% PEG treatment (P < 0.05). The ratios of radicle to hypocotyl of 20% PEG treatment were significant higher than those of the corresponding controls for both provenances (P < 0.05). These results suggested that Mongolian pine seeds/seedlings had stronger resistance to PEG drought stresses; 10% PGE stress did not significantly influence germination. Natural seeds exhibited more resistance to PEG stress than plantation seeds. It was concluded that drought stress on seed germination might be one cause of obstructed natural regeneration of Mongolian pine plantations on sandy land. It is recommended that natural seeds be used for afforestation, and light drought stress (e.g., 10% PEG stress) may be useful in improving seed germination and the growth of radicles and hypocotyls.