RESUMEN
Developing ionogel electrolytes based on ionic liquid instead of volatile liquid in gel polymer electrolytes is regarded to be effective to diminish safety concerns in terms of overheating and fire. Herein, a zwitterion-based copolymer matrix based on the copolymerization of trimethylolpropane ethoxylate triacrylate (ETPTA) and 2-methacryloyloxyethylphosphorylcholine (MPC, one typical zwitterion) is developed. It is shown that introducing zwitterions into ionogel electrolytes can effectively optimize local lithium-ion (Li+ ) coordination environment to improve Li+ transport kinetics. The interactions between Li+ and bis(trifluoromethanesulfonyl)imide (TFSI- )/MPC lead to the formation of Li+ coordination shell jointly occupied by MPC and TFSI- . Benefiting from the competitive Li+ attraction of TFSI- and MPC, the energy barrier of Li+ desolvation is sharply decreased and thus the room-temperature ionic conductivity can reach a value of 4.4 × 10-4 S cm-1 . Besides, the coulombic interaction between TFSI- and MPC can greatly decrease the reduction stability of TFSI- , boosting in situ derivation of LiF-enriched solid electrolyte interface layer on lithium metal surface. As expected, the assembled Li||LiFePO4 cells deliver a high reversible discharge capacity of 139 mAh g-1 at 0.5 C and good cycling stability. Besides, the pouch cells exhibit a steady open-circuit voltage and can operate normally under abuse testing (fold, cut), showing its outstanding safety performance.
RESUMEN
High-entropy alloys (HEAs) are attracting increased attention as an alternative to noble metals for various catalytic reactions. However, it is of great challenge and fundamental importance to develop spatial HEA heterostructures to manipulate d-band center of interfacial metal atoms and modulate electron-distribution to enhance electrocatalytic activity of HEA catalysts. Herein, an efficient strategy is demonstrated to construct unique well-designed HEAs spatial heterostructure electrocatalyst (HEA@Pt) as bifunctional cathode to accelerate oxygen reduction and evolution reaction (ORR/OER) kinetics for Li-O2 batteries, where uniform Pt dendrites grow on PtRuFeCoNi HEA at a low angle boundary. Such atomically connected HEA spatial interfaces engender efficient electrons from HEA to Pt due to discrepancy of work functions, modulating electron distribution for fast interfacial electron transfer, and abundant active sites. Theoretical calculations reveal that electron redistribution manipulates d-band center of interfacial metal atoms, allowing appropriate adsorption energy of oxygen species to lower ORR/OER reaction barriers. Hence, Li-O2 battery based on HEA@Pt electrocatalyst delivers a minimal polarization potential (0.37 V) and long-term cyclability (210 cycles) under a cut-off capacity of 1000 mAh g-1 , surpassing most previously reported noble metal-based catalysts. This work provides significant insights on electron-modulation and d-band center optimization for advanced electrocatalysts.
RESUMEN
The commercialization of MXenes as anodes for lithium-ion batteries is largely impeded by low initial coulombic efficiency (ICE) and unfavorable cycling stability, which are closely associated with defects such as Ti vacancies (VTi ) in Ti3 C2 MXenes. Herein, an effective strategy is developed to deactivate VTi defects by in situ growing Al2 O3 nanoclusters on MXenes to alleviate the irreversible electrolyte decomposition and Li dendrites formation trend induced by defects, improving ICE and cycling stability. Furthermore, it is revealed that excessively lithiophilic VTi defects would impede Li ions diffusion due to their strong adsorption, leading to a locally nonuniform Li flux to these "hot spots," setting scene for the formation of Li dendrites. The Al2 O3 nanoclusters anchored on VTi sites can not only improve Li diffusion kinetics but also promote the homogeneous solid electrolyte interphase formation with small charge transfer resistance, achieving uniform Li deposition in a smaller overpotential without formation of Li dendrites. As expected, Ti3 C2 @Al2 O3 -11 electrode delivers a high ICE of 76.6% and an outstanding specific capacity of 285.5 mAh g-1 after 500 cycles, which is much higher than that of pristine Ti3 C2 sample. This work sheds light on modulating defects for high-performance energy storage materials.
RESUMEN
Taking into consideration the advantages of the highly theoretical capacity of antimony (Sb) and abundant surface redox reaction sites of Na+ pre-intercalated 3D porous Ti3C2Tx (Na-Ti3C2Tx) architectures, we elaborately designed the Sb/Na-Ti3C2Tx hybrid with Sb nanoparticles homogeneously distributed in 3D porous Na-Ti3C2Tx architectures through a facile electrostatic attraction and carbothermic reduction process. Na-Ti3C2Tx architectures with more open structures and larger active specific surface area not only could certainly alleviate volume changes and hinder the aggregation of Sb nanoparticles in the cycling process to improve the structural stability but also significantly strengthen the electron-transfer kinetics and provide unblocked K+ diffusion channels to promote ionic/electronic transport rate. Furthermore, the ultrafine Sb nanoparticles could efficiently shorten K+ transport distance and expose more accessible active sites to improve capacity utilization. DFT calculations further indicate that the Sb/Na-Ti3C2Tx anode effectively decreases the adsorption energy of K+ and accelerates the potassiation process. Benefiting from the synergistic effect, it exhibits an outstanding specific capacity of 392.2 mAh g-1 at 0.1 A g-1 after 450 cycles and a stable capacity reservation with a capacity fading rate of 0.03% per cycle at 0.5 A g-1. Our work may encourage further research on advanced MXene-based hybrid materials for high-performance PIBs.
