Monodisperse Antimony Nanocrystals for High-Rate Li-ion and Na-ion Battery Anodes: Nano versus Bulk

Abstract

We report colloidal synthesis of antimony (Sb) nanocrystals with mean size tunable in the 10-20 nm range and with narrow size distributions of 7-11%. In comparison to microcrystalline Sb, 10 and 20 nm Sb nanocrystals exhibit enhanced rate-capability and higher cycling stability as anode materials in rechargeable Li-ion and Na-ion batteries. All three particle sizes of Sb possess high and similar Li-ion and Na-ion charge storage capacities of 580-640 mAh g(-1) at moderate charging/discharging current densities of 0.5-1C (1C-rate is 660 mA g(-1)). At all C-rates (0.5-20C, e.g. current densities of 0.33-13.2 Ag(1-)), capacities of 20 nm Sb particles are systematically better than for both 10 nm and bulk Sb. At 20C-rates, retention of charge storage capacities by 10 and 20 nm Sb nanocrystals can reach 78-85% of the low-rate value, indicating that rate capability of Sb nanostructures can be comparable to the best Li-ion intercalation anodes and is so far unprecedented for Na-ion storage.

In Situ Carbon-Doped Mo(Se0.85S0.15)2Hierarchical Nanotubes as Stable Anodes for High-Performance Sodium-Ion Batteries

“…[1][2][3][4][5][6] However, Na + ions have a larger radius than Li + ions, which makes reversible and rapid Na + ion intercalation/extraction and transport in host materials more diffi cult, leading to problems such as large voltage polarization, poor cycling, and rate performance. [1][2][3][4][5][6] Many recent efforts have been devoted to exploring potential anode materials for SIBs, such as P, [ 7 ] Sn, [ 8 ] Sb, [ 9,10 ] SnSb, [ 11 ] SnO 2 , [ 12,13 ] Fe 2 O 3 , [ 14,15 ] CuO, [ 16 ] MoO 3 , [ 17 ] Na 2 Ti 3 O 7 , [ 18,19 ] Sb 2 S 3 , [ 20 ] FeS 2 , [ 21 ] Ni 2 S 3 , [ 22 ] SnS 2 , [23][24][25] WS 2 , [ 26 ] carbon-based materials, [27][28][29] etc. The anode materials with alloying mechanisms (e.g., Sn and Sb) or metal oxides and sulfi des with conversion mechanisms always have high theoretical capacities, but they suffer from poor cycling performance due to their huge volume and Therefore, it is urgent but of great challenge to fi nd new anode materials for SIBs with both long-term cycling stability and high capacity.…”

Sodium‐Ion Batteries: From Academic Research to Practical Commercialization

“…These cathode materials include layer-structured transition metal oxides, [4][5][6] polyanionic-type compounds, [7,8] Prussian blue analogues, [9,10] and organic-based materials. [11,12] Meanwhile, significant progress has also been made on anode materials for SIBs, and various materials have been explored as promising candidates, including carbonaceous materials, [13][14][15] metals or alloys, [16][17][18][19][20] phosphorus, [21,22] phosphide, [23,24] oxides, [25,26] sulfides, [27,28] and phosphates. [29,30] During the long period of academic research on SIBs, there have been a number of achievements, especially on the active materials and electrolyte.…”

Low‐Cost Metallic Anode Materials for High Performance Rechargeable Batteries

“…Sb nanocrystalls with mean size of 10-20 nm and narrow size distributions of 7-11% were reported as anode materials in LIBs and SIBs by He et al [153] As compared to microstructured Sb, Sb anodes with 10 and 20 nm in diameter exhibited enhanced cycling stability and rate capability, indicating the positive effect of nanosizing strategy for Sb-based anode materials. First-cycle CEs of 50-60% for nanosized Sb and 70-75% for bulk Sb in SIBs and 30-40% for nanosized Sb and 70-75% for bulk Sb in LIBs were obtained.…”

“…To overcome the deteriorations of Sb anode, modification strategies including nanosizing strategy, [153] hollow structure design, [154] Sb-based alloy/intermetallic design (including Ag 3 Sb, [155] AlSb, [156,157] Mg 3 Sb 2 , [158] Sn-Sb, [159] Cu 2 Sb, [160][161][162][163] Mo 3 Sb 7 , [164] NiSb, [165] ), Sb/C composite design (including Sb/C nanofiber, [166] Sb/C microsphere, [167] Sb/C nanosheet, [168] Sb/graphene, [169][170][171] Sb/3D carbon network [172] ), have been developed. Sb nanocrystalls with mean size of 10-20 nm and narrow size distributions of 7-11% were reported as anode materials in LIBs and SIBs by He et al [153] As compared to microstructured Sb, Sb anodes with 10 and 20 nm in diameter exhibited enhanced cycling stability and rate capability, indicating the positive effect of nanosizing strategy for Sb-based anode materials.…”

“…These results are consistent with the higher specific surface area of nanosized materials as well as with thinner SEI reported for SIBs. [153] By a galvanic replacement process, hollow Sb nanospheres were successfully prepared and utilized as anode materials in LIBs and SIBs. [173] The hollow nanostructure is favorable to buffer the volume change during alloying/de-alloying and shorten the ion/electron diffusion length.…”