Enhanced Air and Electrochemical Stability of Li7P2.9Ge0.05S10.75O0.1 Electrolytes with High Ionic Conductivity for Thiophosphate-Based All-Solid-State Batteries.
ACS Appl Mater Interfaces
; 14(35): 39985-39995, 2022 Sep 07.
Article
in En
| MEDLINE
| ID: mdl-36000918
ABSTRACT
Sulfide solid electrolytes (SSEs) show tremendous potential to realize high-energy-density secondary batteries and offer distinguishing safety features over the traditional liquid-electrolyte-based system. However, their installation is hindered by the air sensitivity and substandard interfacial compatibility with Li-metal anodes. Herein, an aliovalent P5+/Ge4+ and isovalent S2-/O2- cosubstitution strategy increases the σLi+ to 4.77 mS cm-1, which is associated with the lowest activation energy (18.66 kJ mol-1). Impressively, with limited substitution of P/Ge and S/O in Li7P3S11, the derived electrolytes largely suppressed the structural hydrolysis in the air. Furthermore, the Li//Li cell with novel Li7P2.9Ge0.05S10.75O0.1 SSEs realized Li plating/stripping over 100 h at 0.1 mA cm-2/0.1 mAh cm-2 @ RT, with the lowest overpotential at â¼5 mV. Next, ex situ X-ray photoelectron spectroscopy (XPS) quantified the electrochemical decomposition of the Li7P3S11/LiNbO3@NCA interface during cell operation. XPS results confirmed better thermodynamic stability between LiNbO3@NCA and L7P3S11 after GeO2 substitution. Accordingly, the LiNbO3@NCA/Li7P2.9Ge0.05S10.75O0.1/Li-In cell performed remarkably; first discharge capacity, 158.9 mAh g-1; capacity retention, 89%; and Coulombic efficiency, â¼100% after 50 cycles @ 0.064 mA cm-2 and even at 0.3 mA cm-2 versus the first discharge capacity and retention (129.4 mAh g-1 and 75.73%) after 70 cycles @ RT. These remarkable results could be attributable to the excellent σLi+, chemical/electrochemical stability toward LiNbO3@NCA, and meager interfacial resistance, essential for the practical application of sulfide-based batteries.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
ACS Appl Mater Interfaces
Journal subject:
BIOTECNOLOGIA
/
ENGENHARIA BIOMEDICA
Year:
2022
Document type:
Article
Affiliation country:
China