A Highly Stable Li‐Organic All‐Solid‐State Battery Based on Sulfide Electrolytes

Abstract

Sulfide solid electrolytes with high conductivity that is close to that of liquid electrolyte have been considered to be one of the most promising electrolytes for all‐solid‐state lithium batteries (ASSLBs). Unfortunately, the narrow electrochemical windows of sulfide electrolyte and contact loss at the interface upon cycles much limits the application of sulfide‐based ASSLBs. In this work, an organic quinone cathode, 5,7,12,14‐pentacenetetrone (PT), is used to fabricate an ASSLB with a sulfide electrolyte of glass ceramic 70Li2S‐30P2S5 (LPS). Based on the various in situ/ex situ analyses, it is successfully demonstrated that the decomposition of LPS is negligible and the corresponding effects on interfacial impedance are reversible with optimized carbon additives. In addition, the inherent low Young's modulus of the PT electrode efficiently prevents the contact loss at the interface. As a result, the PT‐based ASSLBs deliver a high specific capacity (312 mAh g−1) and an excellent capacity retention (90.6%) over 500 cycles which is superior to previous reports. Moreover, a carbon‐free ASSLB is constructed by employing Mo6S8 as conductive additives in a PT‐based cathode, which shows an improved rate performance and a long life.

Electrolytes in Organic Batteries

“…327 Recently, the chemical and electrochemical compatibilities between PT electrodes and Li 7 P 3 S 11 electrolytes were investigated, in depth, by spectroscopic and electrochemical characterizations. 75 According to in situ XRD results, no new peak or halos developed during the first cycle, indicating a lack of detectable decomposition products (Figure 22h). With continued cycling, the peak intensity associated with the electrolyte Li 7 P 3 S 11 was observed to decrease.…”

“…(h) In situ XRD patterns of all-solid-state Li-PT cell during the first discharge/charge cycle. Reproduced with permission from ref . Copyright 2022 Wiley-VCH.…”

“…In particular, aqueous Zn-organic batteries have been successfully applied in wearable electronic devices . Furthermore, in solid-state organic batteries, the inherent low Young’s modulus of organic electrode materials could efficiently prevent the contact loss at the interface between the electrode and the solid-state electrolyte, while maintaining intimate interfacial contact during cell cycling. , In contrast, inorganic electrode materials with high Young’s modulus are less likely to maintain adequate electrochemical performance after repeated cycling. The degradation in capacity for inorganic electrode materials is generally attributed to local stress caused by intercalation related volume changes which may lead to cracks at the interface, and eventually result in the loss of mechanical contact with the substrate, particle level cracking, and electronic isolation. , …”

“…Considering that traditional hand-milling and ball-milling methods cannot effectively reduce the size of the active material, the cryomilling technique is beneficial to decreasing the size of the active materials and suppress side reactions between Li 3 PS 4 and the PTO electrode simultaneously, thus improving the electrochemical performance of the battery . Recently, the chemical and electrochemical compatibilities between PT electrodes and Li 7 P 3 S 11 electrolytes were investigated, in depth, by spectroscopic and electrochemical characterizations . According to in situ XRD results, no new peak or halos developed during the first cycle, indicating a lack of detectable decomposition products (Figure h).…”

Progress and Perspective of Glass-Ceramic Solid-State Electrolytes for Lithium Batteries

“…Wang et al [ 127 ] designed a Li-metal negative electrode with PEO-50000 (LiTFSI) film and obtained good interface by assembling into a cell of Li-PEO-500000 (LiTFSI)/LAGP-PEO1/LiMFP, as shown in Figure 8 . Zhou et al [ 128 ] then used organic quinone cathode 5,7,12,14-pentaerythritone (PT) to prepare an ASSLIB with a glass-ceramic 70Li 2 S-30P 2 S 5 sulfide electrolyte, which exhibited excellent rate performance and cycling performance. The reason for this is that the inherently low Young’s modulus of the PT electrode effectively prevents contact loss at the interface.…”