Inducing the Formation of In Situ Li₃N-Rich SEI via Nanocomposite Plating of Mg₃N₂ with Lithium Enables High-Performance 3D Lithium-Metal Batteries

Abstract

Lithium metals fit the growing demand of high-energy density rechargeable batteries because of their high specific capacity and low redox potential. However, the lithium-metal anodes are abandoned because of various defects. In this study, we apply composite plating into the protection of lithium-metal anodes. We confirmed that the Mg 3 N 2 nanoparticle dispersed in the ether electrolyte can be easily composite-plated with lithium, resulting in a flat, dense, and dendrite-free lithium deposition layer during the electrodeposition process. In addition, the Mg 3 N 2 plated in the lithium metal phase would react with lithium and then generate a Li 3 N-rich solid electrolyte interphase (SEI) layer, mitigating continuous side reactions of the electrolyte on the Li metal. In addition, another product of the reaction is Mg which can work as lithiophilic sites in electrodeposition. The combined effect of the two fields can effectively improve the performance of lithium metal anodes. The Li 3 N-rich SEI layer would grow well on the surface of the three-dimensional (3D) lithium anode by composite plating. Furthermore, composite plating with the Mg 3 N 2 -containing electrolyte is a viable route that can be used for various 3D current collectors easily with a small volume effect. Here, we show that the composite plating 3D lithium metal anode is successfully applied in the Li−S battery with a long lifetime.

Review on Li Deposition in Working Batteries: From Nucleation to Early Growth

“…www.advmat.de www.advancedsciencenews.com is the rate-determining step of Li + diffusion process. Enhancing the amount of higher ionic conductivity of the SEI components (Li 2 S/Li 2 Se, [101] Li 3 N, [102] LiI, [103] Li 3 PS 4 , [104] and Li 2 TeS 3 [105] ) can maintain the Li deposition under the reaction-controlled condition and therefore regulating the compact Li deposition morphology. Liu et al employed a Li + conductive Li 2 S/Li 2 Se protection layer to protect Li anode with a dendrite-free deposition behavior over 900 h. [101] Liang and co-workers fabricated a Li 7 P 2 S 8 I [95] Copyright 2013, American Chemical Society.…”

“…The ionic conductivity of SEI is several orders of magnitude lower than of the liquid electrolyte, so the Li + diffusion through the SEI is the rate‐determining step of Li + diffusion process. Enhancing the amount of higher ionic conductivity of the SEI components (Li 2 S/Li 2 Se, [ 101 ] Li 3 N, [ 102 ] LiI, [ 103 ] Li 3 PS 4 , [ 104 ] and Li 2 TeS 3 [ 105 ] ) can maintain the Li deposition under the reaction‐controlled condition and therefore regulating the compact Li deposition morphology. Liu et al.…”

Coupling a Sponge Metal Fibers Skeleton with In Situ Surface Engineering to Achieve Advanced Electrodes for Flexible Lithium–Sulfur Batteries

“…on 3D skeletons to induce uniform Li deposition and growth during electrodeposition or molten infiltration process. For the other thing, fabricating a robust SEI layer by chemically adding electrolyte additives (e.g., fluoroethylene carbonate (FEC), [ 17,24 ] LiNO 3 , [ 17,37 ] and Cs +[ 38 ] ) or physically designing artificial buffer layers (Li 3 N, [ 39,40 ] AlN, [ 40,41 ] polyuria, [ 42 ] etc.) on the surface of Li metal to protect the interface between reactive Li and electrolyte is also credible.…”

Gradient Solid Electrolyte Interphase and Lithium‐Ion Solvation Regulated by Bisfluoroacetamide for Stable Lithium Metal Batteries

“…[9] Up to now,e xtensive strategies have been made to suppress the formation of Li dendrites and protect the structural stability of cathode materials. [10][11][12][13][14][15][16][17][18][19] Among those, regulating the composition and structure of SEI is the most effective way because the SEI plays ac rucial role in battery performance. [20] It is known that there are two distinct SEI nanostructures (i.e., mosaic and multilayer structures) [21,22] and the uniform Li striping/plating can be achieved in the more ordered multilayer SEI structure.…”