Influence of polymorphism on the electrochemical behavior of M Sb negative electrodes in Li/Na batteries

The Electrochemical Sodiation of Sb Investigated by Operando X-ray Absorption and 121Sb Mössbauer Spectroscopy: What Does One Really Learn?

“…The structures of pure antimony and of the two known Na-Sb intermetallics (i.e., NaSb and hexagonal Na 3 Sb) are shown in Figure 1 together with their respective experimental XAS and 121 Sb Mössbauer spectroscopy signatures. The XRD patterns (see Supplementary Materials) were successfully refined in the expected P63/mmc (cell parameters a=b=5.35(6) Å, and c=9.49(2) Å) and P21/c (cell parameters a=6.78(7) Å, b=6.33(6) Å, c=12.47(2) Å and β=117.51(4) • ) space groups for Na 3 Sb and NaSb, respectively, in very good agreement with the structures reported in the Na-Sb phase diagram and with previous reported theoretical calculations [6,10,27,28]. The 121 Sb Mössbauer spectrum of Sb collected at 78 K was fitted using a quadrupole split component, which provided an isomer shift of −11.42(3) mm s −1 and a small quadrupole splitting of 4.3(8) mm s −1 , (see Table 1) in agreement with published data and with the slightly distorted octahedral Sb site in Sb metal [24].…”

“…In a recent work, however, phase diagram calculations made by our group have pointed out the existence of Na x Sb phases close to the two-phase reactions (Sb → NaSb → Na 3 Sb) confirming the complexity of sodiation mechanism [6]. Moreover, short-range probing spectroscopic techniques such as operando Pair Distribution Function (PDF) and ex situ 23 Na Solid State Nuclear Magnetic Resonance (NMR) were applied in a subsequent study to investigate the formation of intermediates upon sodiation of Sb [7].…”

Antimony (Sb)-Based Anodes for Lithium–Ion Batteries: Recent Advances

“…Chang et al reported that the lithium insertion and extraction follows different pathways. Three distinctive phases (Sb, Li 2 Sb and Li 3 Sb) are reported in a Li and Sb alloy [11,12]. The Sb exist in the rhombohedral structure, Li 2 Sb is hexagonal and Li 3 Sb is cubic.…”

“…Though it is fundamentally interesting to study these systems, the very high-volume changes associated with these systems (390% for Na, 407% for K) make it difficult to stabilize the electrodes and must be addressed accordingly [15]. (Sb, Li2Sb and Li3Sb) are reported in a Li and Sb alloy [11,12]. The Sb exist in the rhombohedral structure, Li2Sb is hexagonal and Li3Sb is cubic.…”

SnSb–ZnO composite materials as high performance anodes for lithium-ion batteries

“…Alloys which were formed by lithium with many metals M (M ¼ Mg, Ca, Al, Sn, Pb, As, Sb, Bi, Pt, Ag, Au, Zn, Cd, Hg) can be used as anode materials for lithium ion battery. For example, lithium alloying (or lithium insertion) materials such as Sn, [1][2][3][4][5][6][7][8] SnO 2 [9][10][11] and Sb [12][13][14][15][16] have gained attention as potential candidates due to their high theoretical capacities and energy density. However, the large volume change of the anode materials during charge/discharge processes will easily cause cracking or pulverization, and consequently affect the cycling performance of electrode.…”