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

Abstract

b-Li 10 P 4 N 10 and Li 13 P 4 N 10 X 3 with X = Cl, Br have been synthesized from mixtures of P 3 N 5 ,L i 3 N, LiX,L iPN 2 ,a nd Li 7 PN 4 at temperatures below 850 8C. b-Li 10 P 4 N 10 is the lowtemperature polymorph of a-Li 10 P 4 N 10 and crystallizes in the trigonal space group R3. It is made up of non-condensed [P 4 N 10 ] 10À T2 supertetrahedra, whicha re arrangedi ns phalerite-analogous packing. Li 13 P 4 N 10 X 3 (X = Cl, Br) crystallizes in the cubic space group Fm " 3m.B oth isomorphic compounds comprise adamantane-type [P 4 N 10 ] 10À ,L i + ions, and halides, which form octahedra. These octahedra build up af ace-centered cubic packing,w hose tetrahedral voids are occupied by the [P 4 N 10 ] 10À ions. The crystal structures have been elucidated from X-ray powder diffraction data and corroborated by EDX measurements, solid-state NMR, and FTIR spectroscopy.F urthermore,w eh ave examined the phase transition between a-a nd b-Li 10 P 4 N 10 .T oc onfirm the ionic character, the migration pathways of the Li + ions have been evaluated and the ion conductivity and its temperature dependence have been determined by impedance spectroscopy.X PS measurementsh aveb een carriedo ut to analyze the stability with respect to Li metal.

Ammonothermal Synthesis, Optical Properties, and DFT Calculations of Mg2PN3 and Zn2PN3

“…Consequently,o nly af ew phosphorus nitrides, for example, Ca 2 PN 3 or Li 10 P 4 N 10 ,w ere synthesized at ambient pressure. [15][16][17] To prevent decomposition of P 3 N 5 ,h igh-pressure synthesis techniquesi nt he 10-20 GPa range,s uch as the multi-anvil approach, have been used. Thereby,n umerousP -N-compounds like SrP 2 N 4 or LiNdP 4 N 8 became accessible.…”

Nitridophosphates: A Success Story of Nitride Synthesis

“…[20] Through the nitride route,v arious lower-condensed (k < 1/2) lithium nitridophosphates have been prepared:L i 47 B 3 P 14 N 42 , Li 12 P 3 N 9 , a/b-Li 10 P 4 N 10 ,L i 13 P 4 N 10 X 3 (X = Cl, Br), and Li 7 PN 4 . [7,10,[21][22][23] Li 3 Ni ss uspected to be af lux in these reactions,t hus coining the term Li 3 Ns elf-flux.…”

Crystalline Nitridophosphates by Ammonothermal Synthesis

“…[24][25][26][27]31] An exemplary Rietveld plot of Ca 2 PN 3 is illustrated in Figure2.T he Rietveld plots of a-Li 10 P 4 N 10 , b-Li 10 P 4 N 10 ,L i 18 P 6 N 16 ,a nd LiPN 2 can be found in the Supporting Information (Figures S1 andS 6, Supporting Information). [24][25][26][27]31] An exemplary Rietveld plot of Ca 2 PN 3 is illustrated in Figure2.T he Rietveld plots of a-Li 10 P 4 N 10 , b-Li 10 P 4 N 10 ,L i 18 P 6 N 16 ,a nd LiPN 2 can be found in the Supporting Information (Figures S1 andS 6, Supporting Information).…”

“…[19][20][21][22] Nitridophosphates are built up from PN 4 tetrahedra and their tetrahedra-based networks can be characterizedb yt he degree of condensation k = n(T)/n(X), which represents the atomic ratio of tetrahedral centers (T = P) and coordinating atoms (X = N). [24] For 1/4 < k < 1/2, partially condensed PN 4 tetrahedra may form complex anions, such as adamantane-like groups (a-Li 10 P 4 N 10 , b-Li 10 P 4 N 10 ), [25,26] chain structures (e.g. Li 7 PN 4 ) [23] possessadegree of condensation of k = 1/4, whereas highly condensed frameworks feature k !…”

“…[24][25][26][27]29] Following Le Chatelier's principle, thermal decomposition, however,c an be suppressed by applyingp ressure. Ca 2 PN 3 , a-Li 10 P 4 N 10 , b-Li 10 P 4 N 10 ,L iPN 2 or Mg 2 PN 3 ).…”