Two-Dimensional Hybrid Halide Perovskite as Electrode Materials for All-Solid-State Lithium Secondary Batteries Based on Sulfide Solid Electrolytes

Abstract

All-solid-state lithium secondary battery using two-dimensional hybrid halide perovskite (2D-HHP) (CH3(CH2)2NH3)2(CH3NH3)2Pb3Br10 as electrode materials and sulfide-based solid electrolyte is fabricated for the first time. Although large amounts of lithium-ion conductor have been mixed in the electrodes of the all-solid-state batteries based on sulfide solid electrolytes, the high lithium-ion coefficient of the 2D-HHP, around 10 −7 cm 2 s −1 , allowed the suitable operation of the batteries without the addition of any lithium-ion conductor into the electrode. The lithium-ion diffusion in the electrode improves with the temperature, showing a better performance at 100 ºC and keeping a low resistance between electrode/electrolyte interface of 13 Ω. The all-solid-state battery retains a reversible capacity of more than 242 mAh g −1 for 30 cycles at 0.13 mA cm −2 with a negligible capacity fade. The mechanism of the lithium storage into the 2D-HHP electrode material consists of a three-step reaction: Li + insertion/extraction, conversion, and alloying−dealloying reactions.

2D Materials for All‐Solid‐State Lithium Batteries

“…The ASSLB retains 242 mA h g −1 after 30 cycles at 0.13 mA cm −2 . [149] Shi et al applied 2D Co 3 S 4 hexagonal nanosheets as cathodes to improve the interface contact and Li-ion conductivity of ASSLBs. 2D Co 3 S 4 hexagonal nanosheets were used in a liquid-phase method to coat the surface of Li 7 P 3 S 11 (Figure 6d).…”

Halide Perovskite Materials for Energy Storage Applications

“…[ 182 ] Another 2D halide perovskite based on (CH 3 (CH 2 ) 2 NH 3 ) 2 (MA) 2 Pb 3 Br 10 is applied in lithium‐ion batteries, demonstrating a lithium diffusion coefficient of 10 −7 cm 2 s −1 and a capacity of 242 mAh g −1 at 0.13 mA cm −2 ; this is contributed by the three‐stage reactions (lithium insertion/deinsertion, conversion reaction, and Li x Pb alloying/dealloying reaction) ( Figure a). [ 183 ] Both 3D and 2D halide perovskites manipulated by the long organic cations are investigated for lithium batteries in contact with a Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 solid‐state electrolyte. The resulting battery capacities are 153 mAh g −1 for the 3D perovskite material and 149 mAh g −1 for the 2D perovskite material (Figure 8b).…”

“…Reproduced with permission. [ 183 ] Copyright 2019, American Chemical Society. b) 3D and 2D halide perovskites in contact with Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 (LLZTO) electrolyte and LiFePO 4 (LFP).…”

Cathode–Sulfide Solid Electrolyte Interfacial Instability: Challenges and Solutions

“…A 2D-hybrid halide perovskite + Vapor Grown Carbon | LPS | Li-In ASSB showed a reversible capacity of after 30 cycles and a low interfacial resistance between 10-26 Ω cm −2 before and after cycling. This cathode-sulfide interfacial resistance is lower than that of common coated HVTMO cathodes in ASSBs which after an initial cycle can have an interfacial resistance of 125.6-204.2 Ω cm −2 (Fujii et al, 2019;Li et al, 2020a). The hybrid halide perovskite's high ionic conductivity also avoided the need for solid electrolyte powder in the cathode.…”