Phenylboronic Acid Functionalized Calix[4]pyrrole‐Based Solid‐State Supramolecular Electrolyte

Abstract

Solid‐state polymer electrolytes (SPEs) suffer from the low ionic conductivity and poor capability of suppressing lithium (Li) dendrites, which limits their utility in the preparation of all solid‐state Li‐metal batteries (LMBs). We report here a flexible solid supramolecular electrolyte that incorporates a new anion capture agent, namely a phenylboronic acid functionalized calix[4]pyrrole (C4P), into a poly(ethylene oxide) (PEO) matrix. The resulting solid‐state supramolecular electrolyte demonstrated high ionic conductivity (1.9 × 10−3 S cm−1 at 60°C) and a high Li+ transference number (tLi+ = 0.70). Furthermore, the assembled Li|C4P‐PEO‐LiTFSI|LiFePO4 cell allowed for stable cycling over 1200 cycles at 1 C at 60°C, as well as good rate performance. The favorable performance of the C4P‐PEO‐LiTFSI SPE leads us to suggest it could prove useful in the creation of high energy density solid‐state LMBs.This article is protected by copyright. All rights reserved

Multipolar Conjugated Polymer Framework Derived Ionic Sieves via Electronic Modulation for Long‐Life All‐Solid‐State Li Batteries

“…The 0.5 %CNF-COF@PEO electrolyte exhibits a much higher t Li + of 0.81 (Figure 3e) relative to the PEO counterpart (0.22) (Figure S11) and even surpassing most reported PEO-based solid electrolytes involving different functional fillers under comparable conditions. [6,20,21,[23][24][25][47][48][49] As indicated in Figure S3 and S12, at 30 °C, the ionic conductivity and t Li + of the 0.5 %CNF-COF@PEO SPE are 2.65×10 À 5 S cm À 1 and 0.37, higher than 0.5 %CNF-COP@PEO SPE (1.90×10 À 5 S cm À 1 and 0.33), indicating the promoting role of crystalline structure, while 0.5 %CNF-COP@PEO SPE outperforms 0.5 %F-COP @PEO SPE (1.16×10 À 5 S cm À 1 , 0.22) and 0.5 %CN-COP@-PEO SPE (1.46×10 À 5 S cm À 1 , 0.27), implying the key role of -CN and F dual-decoration in Li ion conduction, consistent with the theoretical prediction. Similar trends are also observed in term of the ionic conductivity at 60 °C: CNF-COF@PEO > CNF-COP@PEO > CN-COP@PEO > F-COP@PEO > COP@PEO (Figure S4).…”

“…Such cycling performance metric surpasses almost all literature-reported results using various PEO-based SPE under comparable conditions (Figure 6f). [6,20,21,23,25,48,49,53] Notably, at a higher LFP loading of 4.9 mg cm À 2 , the Li/0.5 %CNF-COF@PEO SPE/LiFePO 4 cell yields an initial capacity of 137.2 mAh g À 1 at 0.2 C with impressive capacity retention of 97.2 % over 500 cycles (Figure 6h). At 50 °C, the 0.5wt %CNF-COP@PEO SPE equipped battery can also perform well and deliver the initial discharge capacity of 89 mAh g À 1 at 2 C with a large retention of 98.8 % after 260 cycles (Figure S27).…”

“…60 °C), when assembled in Li metal batteries. [22][23][24][25] Thus, it is still a huge challenge to simultaneously attain a low filler loading (e.g. < 1 wt %), a good ionic conductivity, a large Li + transference number and long-term interfacial stability for solid polymers electrolytes so as to prolong the lifespan of all-solid-state (ASS) Li metal batteries under high rate operation.…”

“…2 C) and even at elevated temperatures (e.g. 60 °C), when assembled in Li metal batteries [22–25] . Thus, it is still a huge challenge to simultaneously attain a low filler loading (e.g.…”

Interface‐Compatible Gel‐Polymer Electrolyte Enabled by NaF‐Solubility‐Regulation toward All‐Climate Solid‐State Sodium Batteries

“…Extensive strategies are proposed to improve the Na-ion conduction ability of GPEs, grafting groups onto polymer chains to increase Na + transfer sites, [9] using plasticizing additives to reduce T g in polymer chain segments, [10] adding fillers to construct additional carrier transport pathway, [11] synthesizing novel monomer and macromolecular to build special bulk architectures. [12][13][14] These dazzling strategies improve the effect to a certain extent for reinforced ion conduction ability. However, in order to increase to 10 À 2 -10 À 3 S cm À 1 that is comparable to LE and ceramic electrolytes, [15] the existing ion conductivity status of GPEs is still not insufficient and need to be further improved.…”