A flexible electron-blocking interfacial shield for dendrite-free solid lithium metal batteries

Abstract

Solid-state batteries (SSBs) are considered to be the next-generation lithium-ion battery technology due to their enhanced energy density and safety. However, the high electronic conductivity of solid-state electrolytes (SSEs) leads to Li dendrite nucleation and proliferation. Uneven electric-field distribution resulting from poor interfacial contact can further promote dendritic deposition and lead to rapid short circuiting of SSBs. Herein, we propose a flexible electron-blocking interfacial shield (EBS) to protect garnet electrolytes from the electronic degradation. The EBS formed by an in-situ substitution reaction can not only increase lithiophilicity but also stabilize the Li volume change, maintaining the integrity of the interface during repeated cycling. Density functional theory calculations show a high electron-tunneling energy barrier from Li metal to the EBS, indicating an excellent capacity for electron-blocking. EBS protected cells exhibit an improved critical current density of 1.2 mA cm−2 and stable cycling for over 400 h at 1 mA cm−2 (1 mAh cm−2) at room temperature. These results demonstrate an effective strategy for the suppression of Li dendrites and present fresh insight into the rational design of the SSE and Li metal interface.

Lithium‐Metal Anodes Working at 60 mA cm−2 and 60 mAh cm−2 through Nanoscale Lithium‐Ion Adsorbing

“…(b) Galvanostatic cycling profiles of symmetric cells with the LAL/Li electrode or bare Li electrode at 60 mAh cm −2 and 60 mA cm −2 . (c) Comparison of the current density, areal capacity, and cycle life of symmetric cells with the LAL/Li electrode and those of previously reported excellent Li‐metal anodes stabilized by various strategies [27–32] . (d) Li plating/stripping overpotentials of the LAL/Li and bare Li electrodes at a spectrum of current densities from 1 to 60 mA cm −2 .…”

Effectively Regulating More Robust Amorphous Li Clusters for Ultrastable Dendrite‐Free Cycling

“…[6] In addition, isolated Li-dendrites are formed after cycling and gradually turn into the dead Li, which easily accumulated on the electrode surfaces and intensified the polarization of Li electrodes. [6,[10][11][12] Recently, based on the research hotspots of lithium metal challenges, electrolyte modification, [13][14][15] SEI stabilization design, [16][17][18][19][20] solid electrolyte engineering, [21][22][23] threedimensional (3D) structured Li electrodes, [24][25][26][27] lithiophilic nucleation seeds, [26,28] high-strength separators, [29][30][31] etc., are extensively demonstrated. But among them, the Li-phase evolution at the nanoscale during the nucleation and growth has been rarely reported.…”

“…Recently, based on the research hotspots of lithium metal challenges, electrolyte modification, [ 13 , 14 , 15 ] SEI stabilization design, [ 16 , 17 , 18 , 19 , 20 ] solid electrolyte engineering, [ 21 , 22 , 23 ] three‐dimensional (3D) structured Li electrodes, [ 24 , 25 , 26 , 27 ] lithiophilic nucleation seeds, [ 26 , 28 ] high‐strength separators, [ 29 , 30 , 31 ] etc., are extensively demonstrated. But among them, the Li‐phase evolution at the nanoscale during the nucleation and growth has been rarely reported.…”

Lithium‐Metal Anodes Working at 60 mA cm−2 and 60 mAh cm−2 through Nanoscale Lithium‐Ion Adsorbing

“…The discharge product in cathode was proved to be Li 2 O 2 by X-ray diffraction analysis (Figure S34) and presented high reversibility as revealed by its decomposition upon recharge (Figure S35). The LAL/Li-air battery could be stably cycled for over 450 cycles in ambient air with highly overlapped voltage profiles and steady discharge plateaus at % 2.8 V (Figure- [27][28][29][30][31][32] (d) Li plating/stripping overpotentials of the LAL/Li and bare Li electrodes at a spectrum of current densities from 1 to 60 mA cm À2 . (e) Nyquist plots of the symmetric batteries of LAL/Li and bare Li electrodes after the initial cycle and 50 cycles at 60 mA cm À2 and 60 mAh cm À2 , respectively.…”

“…(b) Galvanostatic cycling profiles of symmetric cells with the LAL/Li electrode or bare Li electrode at 60 mAh cm À2 and 60 mA cm À2 . (c) Comparison of the current density, areal capacity, and cycle life of symmetric cells with the LAL/Li electrode and those of previously reported excellent Li-metal anodes stabilized by various strategies [27][28][29][30][31][32]. (d) Li plating/stripping overpotentials of the LAL/Li and bare Li electrodes at a spectrum of current densities from 1 to 60 mA cm À2 .…”