Lithium nitride and related materials case study of the use of modern solid state research techniques☆

Li+ Ion Conductors with Adamantane‐Type Nitridophosphate Anions β‐Li10P4N10 and Li13P4N10X3 with X=Cl, Br

“…Deviations from the expectedr atio can be explained by the presenceo fo xygen in the topmost surfacel ayer of the sample (Supporting Information, Figure S45), which most likely stems from surface hydrolysis during sample transfer or traces of oxygen and water in the UHV chamber.D uring stepwise lithiation, the signal at higher bindinge nergy diminishes. Formation of Li 3 N, as in Li 6 P 3 O 9 N (2 Li 6 P 3 O 9 N + 12 Li!Li 3 PO 4 + Li 4 P 2 O 7 + Li 3 N + 7Li 2 O), during the process cannot be unambiguously verified, as the expected Li 3 Ns ignal (in the range 395-396eV) would be located directly under the signal of b-Li 10 P 4 N 10 or Li 13 P 4 N 10 Cl 3 . [53] However,i n view of the relative decrease in the Ns ignal at higher binding energy,t he formation of Li 3 Ns eems likely.…”

“…After optimization,i tc ould be synthesized according to Equations (1), (2), (3), or (4). For all of these routes,w eu sed a Li 3 Nf lux or self-flux,i no pen Ta crucibles sealed in silica ampoules under argon or nitrogen atmosphere, with different excesses of Li 3 No rL i 7 PN 4 as appropriate. We have already described these synthetic approaches in previous work.…”

“…[1][2][3][4][5][6] Nitridophosphates are of particular interest due to their structural variability.T he ability to form different linking patterns of corner-and/oredge-sharing PN 4 tetrahedra as primary building units leads to av ariety of complex structures and allows materials to be optimized for many purposes. [7][8][9][10][11] Synthetic approaches to nitridophosphates are somewhat challenging due to the limited thermal stability of the starting materials (e.g.,P 3 N 5 decomposes above 850 8C).…”

“…[9,[12][13][14] To date, an umber of lithium nitridophosphates have been obtained at reactiont emperatures below 850 8C. [6,[15][16][17][18][19] Reactiono ft he binary nitrides P 3 N 5 and Li 3 Nb etween 620 and 800 8Cl ed to four lithium nitridophosphates with different complex P/N anions in am atrix of Li + ions. [20][21][22][23] Recently,w e succeeded in expanding this substance class with two new complex P/N anions by using the multianvil technique in combination with the Li 3 Ns elf-flux method.…”

“…[22,24] Li 7 PN 4 (620 8C, ambient pressure) is the lithium nitridophosphate with the lowest P/N atomicr atio and consists of non-condensed [PN 4 ] 7À tetrahedra. [23] Non-condensed [P 3 N 9 ] 12À dreier-rings, [25,26] which are isoelectronic with [Si 3 O 9 ] 6À ,a re observed in Li 12 P 3 N 9 (790 8C, ambient pressure). [22] At 820 8Ca nd 6GPa,t hese non-condensed [P 3 N 9 ] 12À dreier-rings polymerize to infinite zweierchains of corner-sharing PN 4 tetrahedra (Li 4 PN 3 ).…”