Manipulating Interfacial Nanostructure to Achieve High‐Performance All‐Solid‐State Lithium‐Ion Batteries

Abstract

All‐solid‐state lithium‐ion batteries (ASSLIBs) have gained substantial attention worldwide due to their intrinsic safety and high energy density. However, the large interfacial resistance of ASSLIBs, which originates from the interfacial reactions and inferior electrode–electrolyte contact between electrodes and solid electrolytes, dramatically constrains their electrochemical performance. Here a dual shell interfacial nanostructure is rationally designed to enable high‐performance ASSLIBs, in which the inner shell LiNbO3 suppresses the interfacial reactions while the outer shell Li10GeP2S12 enables intimate electrode–electrolyte contact. As a result, the dual shell structured Li10GeP2S12@LiNbO3@LiCoO2 exhibits a high initial specific capacity of 125.8 mAh g−1 (1.35 mAh cm−2) with an initial Coulombic efficiency of 90.4% at 0.1 C and 87.7 mAh g−1 at 1 C. More importantly, in situ X‐ray absorption near edge spectroscopy was performed for the first time to reveal the interfacial reactions between Li10GeP2S12 and LiCoO2. This dual shell nanostructure demonstrates an ideal interfacial configuration for realizing high‐performance ASSLIBs.

Sulfide‐Based Solid‐State Electrolytes: Synthesis, Stability, and Potential for All‐Solid‐State Batteries

“…It is worth noting that in situ and operando techniques have been employed more recently to investigate the sulfide containing interfaces. Particularly, in Section , we reviewed in situ and operando XPS, Raman, and XANES techniques used to study the structural and elemental composition of the reaction products with respect to time or potential. A delicate design of experimental setup was essential.…”

“…Operando Raman, in combination with ex situ XPS and SEM, evaluated the potential‐dependent changes in the reaction products at the SSE/Cu interface . In situ XANES during initial charge/discharge process, assisted by ex situ XPS, characterized the interfacial reactions between LGPS and LCO cathode materials, and proved the necessity of using a LNO coating layer to suppress the interfacial reactions …”

“…e‐4) The first deviation of S K‐edge spectra of one‐shell LNO–LCO/LGPS electrodes. e) Reproduced with permission . Copyright 2019, Wiley‐VCH.…”

Interfacial Reactions in Inorganic All‐Solid‐State Lithium Batteries

“…The SAM images and XPS results (Figure 5c) showed us the spatial separation about LiCl and sulfur‐containing particles LMO/Li 6 PS 5 Cl. To unveil the interfacial reactions between LCO and LGPS, Wang et al [104] . performed in‐situ sulfur K‐edge X‐ray absorption near edge spectroscopy (XANES) (Figure 5d).…”

Advanced Characterization Techniques for Interface in All‐Solid‐State Batteries

“…For the advantages mentioned above, XAS is effective to detect the electronic structure change of cathode materials and interphase change in cathodic interface in ASSBs during or after electrochemical process. [ 128 ] In the ASSBs system with LiMn 2 O 4 cathode and NASICON‐type structure Li 2 O–Al 2 O 3 –SiO 2 –P 2 O 5 –TiO 2 –GeO 2 Li‐ion conductive glass ceramic (LICGC) solid electrolyte, the oxidation of Mn ion contributed from oxygen in the solid electrolyte LICGC and the charge compensation during charge process was detected by ex situ XAS. [ 129 ] Compared with ex situ XAS, in situ XAS was conducted with real‐time measurements of the batteries during electrochemical cycling.…”