Zn(Cu)Si_2+xP₃ Solid Solution Anodes for High‐Performance Li‐Ion Batteries with Tunable Working Potentials

Abstract

Si-based anodes with a stiff diamond structure usually suffer from sluggish lithiation/delithiation reaction due to low Li-ion and electronic conductivity. Here, a novel ternary compound ZnSi 2 P 3 with a cationdisordered sphalerite structure, prepared by a facile mechanochemical method, is reported, demonstrating faster Li-ion and electron transport and greater tolerance to volume change during cycling than the existing Si-based anodes. A composite electrode consisting of ZnSi 2 P 3 and carbon achieves a high initial Coulombic efficiency (92%) and excellent rate capability (950 mAh g −1 at 10 A g −1 ) while maintaining superior cycling stability (1955 mAh g −1 after 500 cycles at 300 mA g −1 ), surpassing the performance of most Si-and P-based anodes ever reported. The remarkable electrochemical performance is attributed to the sphalerite structure that allows fast ion and electron transport and the reversible Li-storage mechanism involving intercalation and conversion reactions. Moreover, the cation-disordered sphalerite structure is flexible to ionic substitutions, allowing extension to a family of Zn(Cu)Si 2+x P 3 solid solution anodes (x = 0, 2, 5, 10) with large capacity, high initial Coulombic efficiency, and tunable working potentials, representing attractive anode candidates for next-generation, high-performance, and low-cost Li-ion batteries.

Species-Dependent Nanostructured Diatom-SiO2 Anodes: A Sustainable Option for Optimizing Electrode Performance

“…Theoretical studies indicate that SiO 2 would react irreversibly with Li ions as an in situ convertible oxide, producing electroactive Si domains dispersed in a matrix of electrochemically inactive species. The buffer phases include Li 2 Si 2 O 5 , Li 4 SiO 4 , Li 2 SiO 3 , and Li 2 O. − The on-site produced Si would further react reversibly with Li, being the main contributor to the reversible storage capacity, whereas the inactive phases would buffer Si volume variations, therefore imparting a higher stability to the anode. − Notably, nanostructures of SiO 2 have been shown to achieve cycling capacities of up to 1500 mAh g –1 . − However, the production of such nanostructures often requires high temperature, pressure, and pH, as well as the deployment of toxic/hazardous chemical agents, which are harmful to the environment.…”

Scalable Synthesis of a Porous Micro Si/Si-Ti Alloy Anode for Lithium-Ion Battery from Recovery of Titanium-Blast Furnace Slag

“…To achieve a balance between capacity and stability, a common strategy is to adjust the ratio of Si to the inactive alloy . Furthermore, incorporating active metals has shown promising potential to enhance both stability and specific capacity, such as Ge and Zn . However, it is worth noting that this modification can also result in alterations in electrochemical behavior, alongside a subsequent increase in cost .…”

“…27 Furthermore, incorporating active metals has shown promising potential to enhance both stability and specific capacity, such as Ge 28 and Zn. 29 However, it is worth noting that this modification can also result in alterations in electrochemical behavior, alongside a subsequent increase in cost. 30 Therefore, the structure design of Si with a porous, alloy skeleton together with a straightforward, costeffective, and scalable preparation method is highly attractive but still difficult.…”

3D carbon-coated stannous sulfide-molybdenum disulfide anodes for advanced lithium-ion batteries

“…Alternative anodes with improved specific capacity and safety have been intensively explored. [4][5][6][7][8][9][10][11][12][13][14] Owing to their superior redox reversibility and high specific capacity, metal sulfides (e.g., FeS, CoS, NiS, and ZnS) have been widely exploited as potential anodes for LIBs. [15][16][17][18][19][20][21][22][23][24] Among them, SnS exhibits one of the highest theoretical Li + storage capacity (1137 mA h g À1 ).…”

“…Alternative anodes with improved specific capacity and safety have been intensively explored. 4–14 Owing to their superior redox reversibility and high specific capacity, metal sulfides ( e.g. , FeS, CoS, NiS, and ZnS) have been widely exploited as potential anodes for LIBs.…”