Bimetallic MOFs‐Derived NiFe2O4/Fe2O3 Enabled Dendrite‐free Lithium Metal Anodes with Ultra‐High Area Capacity Based on An Intermittent Lithium Deposition Model

• Published in: ChemSusChem 2024-11, Vol.17 (21), p.e202400569-n/a
• Main Authors: Wang, Mengting, Wei, Tao, Lu, Jiahao, Guo, Xingtong, Sun, Cheng, Zhou, Yanyan, Su, Chao, Chen, Shanliang, Wang, Qian, Yang, Ruizhi
• Format: Article
• Language: English
• Subjects: Anodes; bimetallic metal-organic frameworks (mofs); Bimetals; Density functional theory; Electrodeposition; high area capacity; intermittent deposition model; Iron compounds; Lithium; lithium metal anode (LMA); Metal-organic frameworks; Nickel compounds; Nickel ferrites; Three dimensional composites; three-dimensional (3D) conductive skeleton
• ISSN: 1864-5631; 1864-564X; 1864-564X
• DOI: 10.1002/cssc.202400569

In practical operating conditions, the lithium deposition behavior is often influenced by multiple coupled factors and there is also a lack of comprehensive and long‐term validation for dendrite suppression strategies. Our group previously proposed an intermittent lithiophilic model for high‐performance three‐dimensional (3D) composite lithium metal anode (LMA), however, the electrodeposition behavior was not discussed. To verify this model, this paper presents a modified 3D carbon cloth (CC) backbone by incorporating NiFe2O4/Fe2O3 (NFFO) nanoparticles derived from bimetallic NiFe‐MOFs. Enhanced Li adsorption capacity and lithiophilic modulation were achieved by bimetallic MOFs‐derivatives which prompted faster and more homogeneous Li deposition. The intermittent model was further verified in conjunction with the density functional theory (DFT) calculations and electrodeposition behaviors. As a result, the obtained Li‐CC@NFFO||Li‐CC@NFFO symmetric batteries exhibit prolonged lifespan and low hysteresis voltage even under ultra‐high current and capacity conditions (5 mA cm−2, 10 mAh cm−2), what's more, the full battery coupled with a high mass loading (9 mg cm−2) of LiFePO4 cathode can be cycled at a high rate of 5 C, the capacity retention is up to 95.2 % before 700 cycles. This work is of great significance to understand the evolution of lithium dendrites on the 3D intermittent lithiophilic frameworks. In this study, we employed the Li‐affinity modification of the Li‐phobic CC skeleton by NiFe bimetallic MOFs derivatives for lithium metal prestorage, and achieved a uniform deposition effect through the synergistic effect of bimetallic MOFs derivatives. Furthermore, we developed and validated a new deposition model, the intermittent deposition model, through DFT calculation and demonstration of lithium electroplating morphology.