ABSTRACT
Though considerable Mg-doped layered cathodes have been exploited, some new differences relative to previous reports can be concluded by doping a heavy dose of Mg via two rational strategies. Unlike the common unit cell of the P63/mmc group by X-ray diffraction, neutron diffraction reveals a large supercell of the P63 group and enhanced ordering for Na11/18Mg1/18[Ni1/4Mg1/9Mn11/18]O2 with Mg occupying both the Na and Mn sites. Compared with only one obvious voltage plateau of Na0.5[Ni0.25Mn0.75]O2 (NNM), Na11/18Mg1/18[Ni1/4Mg1/9Mn11/18]O2 (NMNMM) shows more severe voltage plateaus but with excellent electrochemical performance. Na0.5[Mg0.25Mn0.75]O2 (NMM) with Mg only occupying the Ni site displays a highly reversible whole-voltage-range oxygen redox chemistry and smooth voltage curves without any voltage hysteresis. Cationic Ni2+/Ni4+ couples are responsible for the charge compensations of NNM and NMNMM, while only the oxygen anionic reaction accounts for the capacity of NMM between 2.5 and 4.3 V. Interestingly, the Mn3+/Mn4+ pair contributes all capacity for all cathodes between 1.5 and 2.5 V. All cathodes undergo a double-phase mechanism: an irreversible P2-O2 phase transition for NNM, an enhanced reversible P2-O2 phase transition for NMNMM, and a highly reversible P2-OP4 phase transition for NMM. In addition, the designed cathodes display excellent rate capability and long-term cycling stability but with a large difference in the various voltage ranges of 2.5-4.3 and 1.5-2.5 V, respectively. This work provides a good understanding of ion doping and some new insights into exploiting high-performance materials.
ABSTRACT
We now report that some chiral compounds, like alcohols, which are not sterically hindered atropisomers nor epimer mixtures, exhibit two sets of simultaneous NMR spectra in CDCl3. Some other chiral alcohols also simultaneously exhibit two different NMR spectra in the solid state because two different conformers, A and B had different sizes because their corresponding bond lengths and angles are different. These structures were confirmed in the same solid state by X-ray. We designate these as pseudo-resonance for a compound exhibiting several different corresponding lengths that simultaneously coexist in the solid state or liquid state. Variable-temperature NMR, 2D NMR methods, X-ray, neutron diffraction, IR, photo-luminesce (PL) and other methods were explored to study whether new aggregation states caused these heretofore unknown pseudo-resonance structures. Finally, eleven chiral alcohols or diols were found to co-exist in pseudo-resonance structures by X-ray crystallography in a search of the CDS database.
ABSTRACT
Copper-doped (Tb0.861Mn0.121)MnO3-δ has been synthesized by the conventional solid state reaction method. X-ray, neutron, and electron diffraction data indicate that they crystallize in Pnma space group at room temperature. Two magnetic orderings are found for this series by neutron diffraction. One is the ICAM (incommensurate canted antiferromagnetic) ordering of Mn with a wave vector qMn = (â¼0.283, 0, 0) with a ≈ 5.73 Å, b ≈ 5.31 Å, and c ≈ 7.41 Å, and the other is the CAM (canted antiferromagnetic) ordering of both Tb and Mn in the magnetic space group Pn'a21' with a ≈ 5.73 Å, b ≈ 5.31 Å, and c ≈ 7.41 Å. A dielectric peak around 40 K is found for the samples doped with Cu, which is higher than that for orthorhombic TbMnO3.
