High Voltage Magnesium-ion Battery Enabled by Nanocluster Mg₃Bi₂ Alloy Anode in Noncorrosive Electrolyte

Abstract

Currently, developing high voltage (beyond 2 V) rechargeable Mg-ion batteries still remains a great challenge owing to the limit of corrosive electrolyte and low compatibility of anode material. Here we report a facile one step solid state alloying route to synthesize nanoclustered MgBi alloy as a high-performance anode to build up a 2 V Mg-ion battery using noncorrosive electrolyte. The fabricated nanoclustered MgBi anode delivers a high reversible specific capacity (360 mAh g) with excellent stability (90.7% capacity retention over 200 cycles) and high Coulombic efficiency (average 98%) at 0.1 A g. The good performance is attributed to the stable nanostructures, which effectively accommodate the reversible Mg ion insertion/deinsertion without losing electric contact among clusters. Significantly, the nanoclustered MgBi anode can be coupled with high voltage cathode Prussian Blue to assemble a full cell using noncorrosive electrolyte, showing a stable cycling (88% capacity retention over 200 cycles at 0.2 A g) and good rate capability (103 mAh g at 0.1 A g and 58 mAh g at 2 A g). The energy and power density of the as-fabricated full cell can reach up to 81 Wh kg and 2850 W kg, respectively, which are both the highest values among the reported Mg-ion batteries using noncorrosive electrolytes. This study demonstrates a cost-effective route to fabricate stable and high voltage rechargeable Mg-ion battery potentially for grid-scale energy storage.

Alloy Anode Materials for Rechargeable Mg Ion Batteries

“…These findings and understandings promoted an intensive follow‐up work on Mg–Bi alloy anodes by a number of groups (e.g., He et al, [ 159 ] Kravchyk et al, [ 152 ] Tan et al [ 160 ] and Penki et al [ 161 ] ). These efforts substantiated the importance of Bi (mostly in nanometric shape morphology) as a most useful substrate for Mg alloy anodes.…”

“…In recent years, the pioneers devoting to alloy anodes have constructed several promising MIB prototypes. These include Sn anode‐1 м Mg(ClO 4 ) 2 /AN electrolyte solution‐Mg x V 2 O 5 cathode, [ 36b ] Mg 2 Sn anode‐0.5 м Mg(TFSI) 2 /diglyme, 0.5 м Mg(TFSI) 2 /PC or 1 м Mg(ClO 4 ) 2 /AN electrolyte solution–V 2 O 5 oxide cathode, [ 137 ] nano Sn anode–0.5 м Mg(ClO 4 ) 2 /AN electrolyte solution–MgMn 2 O 4 spinel cathode, [ 143 ] Mg 3 Bi 2 anode–1 м LiTFSI and 2 м Mg(TFSI) 2 /AN electrolyte solution‐Prussian blue (PB) cathode [ 160 ] and Mg 3 Bi 2 anode–1 м Mg(TFSI) 2 /DME electrolyte solution–S cathode [ 177 ] ) systems as important examples. Theoretical and actual energy densities (Wh Kg −1 ) of promising full MIBs based on alloy anodes have been estimated and compared in Table 1 .…”

“…There are a number of papers that can serve as good examples for references. [ 93,160,178 ] Nguyen and Song [ 137 ] have constructed MIB prototypes based on high voltage/high capacity V 2 O 5 cathode ( Figure 18 a). Very importantly, several conventional electrolytes like 0.5 м Mg(TFSI) 2 /diglyme, 0.5 м Mg(TFSI) 2 /PC, and 1 м Mg(ClO 4 ) 2 /AN demonstrated a reasonable compatibility with Mg 2 Sn anodes.…”

“…Reproduced with permission. [ 160 ] Copyright 2018, American Chemical Society. f) Discharge/charge profiles and cycling stability of Mg 3 Bi 2 //S full cell.…”

Strongly Coupled W2C Atomic Nanoclusters on N/P‐Codoped Graphene for Kinetically Enhanced Sulfur Host

“…With the broad and surging development of energy‐density technologies, atomic nanoclusters have been remarkably deployed to the application of energy storage and conversion in expectation to solve intrinsic problems or make better the performance, such as metal–air batteries . On the other hand, by investigation, a lot of metal oxide/sulfide “nanoclusters” served as electrode materials for lithium/potassium/magnesium ion batteries . Li et al reported the nitrogen‐doped graphene loaded with MoS 2 nanoclusters, which displayed better adhesion effect for sulfur in lithium–sulfur batteries .…”