Dual CuCl doped argyrodite superconductor to boost the interfacial compatibility and air stability for all solid-state lithium metal batteries

• Published in: Nano energy Vol. 90; p. 106542
• Main Authors: Taklu, Bereket Woldegbreal, Su, Wei-Nien, Nikodimos, Yosef, Lakshmanan, Keseven, Temesgen, Nigusu Tiruneh, Lin, Pei-Xuan, Jiang, Shi-Kai, Huang, Chen-Jui, Wang, Di-Yan, Sheu, Hwo-Shuenn, Wu, She-Huang, Hwang, Bing Joe
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 01.12.2021
• Subjects: Air stability; All-solid-state batteries; Dendrite suppression; Li metal compatibility; Lithium argyrodite; Lithium argyrodite; Dendrite suppression; All-solid-state batteries; Air stability; Li metal compatibility
• ISSN: 2211-2855
• DOI: 10.1016/j.nanoen.2021.106542

The decent ductileness, high ionic conductivity, low cost, and versatility over synthesis methods make Li-argyrodite a promising for all-solid-state lithium batteries. However, its serious interfacial incompatibility with Li anode, dendrite growth, and intrinsic air instability impedes its practicability. Herein, we report a CuCl dual doped Li-argyrodite sulfide superb-conductor (Li6+3xP1−xCuxS5−xCl1+x) prepared to overcome these issues via ball-mill free synthesis approach. The maximum Li+ conductivity of 4.34 mS cm−1 at room temperature with ultrawide voltage stability up to 8 V vs. Li/Li+ was achieved in Li6.3P0.9Cu0.1S4.9Cl1.1 (LPSC-1) via a both composite and planar electrode system and can suppress dendrite formation at a current density of 3 mA cm−2 at 50 оC. The symmetrical cell cycled at 0.1 and 1 mA cm−2 also demonstrates remarkable reversibility with negligible overpotential alteration for more than 2400 h and 400 h. An ex-situ XPS and AC impedance analysis proved enhanced interfacial compatibility at Li | SE and achieved a critical current density of 3 mA cm−2. More interestingly, incorporating soft acid Cu in LPSC-1 boosts the air stability and suppresses H2S generation by two-folds. The XRD for the LPSC-1 before and after air exposure proves the decrease in the oxophilicity of the sulfide solid electrolyte. [Display omitted] •Doping soft acid Cu in LPSC boosts the air stability and suppresses H2S generation.•Ultra-high Li metal capability at 0.1 mA cm−2, 1 mA cm−2 and 3 mA cm−2.•Ionic conductivity of 4.34 mS cm−1 at RT with extended voltage stability, 8 V.•Superior dendrite suppression capability with CCD 3 mA cm−2 at 50 оC.•Decrease in oxophilicity with structural stability confirmed via XRD.