Bimetallic metal-organic frameworks (MOFs) have emerged as highly promising anode candidates for next-generation lithium-ion batteries (LIBs) owing to their unique bimetallic synergy and ultrahigh specific surface area. However, their practical deployment is severely hindered by intrinsically low electrical conductivity and persistent interfacial instability. In this work, we report a semiquinone radical (SQ•-)-mediated interfacial engineering strategy through humic acid (HA) functionalization of Zn/Ni bimetallic MOF anodes, enabling superior electrochemical performance in both liquid and all-solid-state lithium-ion batteries. The as-prepared HA-functionalized bimetallic MOFs (HA-ZnNi-BPDC and HA-ZnNi-ATA) deliver exceptionally high reversible specific capacities of 1453.9 and 1355.5 mAh g−1 after 100 cycles at 0.1 A g−1, and retain 867.0 and 838.2 mAh g−1 after 800 cycles at 1 A g−1, respectively. Furthermore, the all-solid-state cell based on the HA-ZnNi-BPDC anode maintains a high specific capacity of 493.7 mAh g−1 at 0.1 A g−1 after 200 cycles, with a capacity retention of 74.9%. Given that the direct utilization of pristine MOFs as anodes in all-solid-state systems remains largely underexplored, our results unequivocally validate the competitive potential of the designed MOF materials. Electron paramagnetic resonance (EPR) investigations confirm the SQ•--mediated interfacial electron/ion transport mechanism responsible for the superior electrochemical performance of HA-ZnNi-MOFs. The ZnNi synergy effectively balances the stability and redox reversibility of SQ•- at the HA-MOF interface. These findings establish a novel bimetallic-radical synergistic paradigm for designing advanced MOF-based electrodes toward high-performance liquid and all-solid-state lithium-ion batteries.

Nanocrystalline metal films are indispensable as conductors in flexible electronics, yet their electrical functionality is frequently compromised by poor fatigue resistance. We propose a gradient nanolayered (GNL) architecture strategy to enhance the fatigue performance of nanocrystalline Ag films. Through a synergistic combination of fatigue experiments, microstructural analyses and molecular dynamics simulations, we systematically compare the fatigue behavior of two Ag/X (X = Al, Mo) GNL systems. Our results demonstrate that fatigue life and damage mechanisms are critically governed by heterophase interface characteristics. The Ag/Al GNL films exhibit exceptional fatigue resistance, with a fatigue life improvement exceeding two orders of magnitude. This enhancement arises from highly stable coherent Ag/Al interfaces, which suppress grain coarsening, alleviate interfacial stress concentration, and promote crack deflection, thereby delaying crack initiation and impeding crack propagation. In contrast, the Ag/Mo GNL films show only a modest (similar to 3-fold) improvement due to the instability of their semi-coherent interfaces, where interfacial shearing and void formation dominate failure. We elucidate this disparity by establishing a direct correlation between damage mechanisms, interface stability, and the crystallographic misorientation of adjacent Ag layers across the heterophase interface. These findings establish GNL architectures as a promising design concept for developing fatigue-resistant metal films in flexible electronics.

MOFs (metal-organic frameworks) have large specific surface area, abundant active sites, and tunable pore structures, making them highly attractive anode materials for lithium-ion batteries. However, their inadequate electrical conductivity and rate performance greatly hinder the further applications of MOFs in field of energy storage. In this study, we present a robust Mn-MOF/HA (humic acid) composite anode material with multilayer nano-sheet structures, synthesized via in-situ compositing HA with Mn-MOF in general hydrothermal reaction. The Mn-MOF derived from hydrothermal reaction shows poor electrochemical stability and low electrical conductivity. The incorporation of HA notably elevates electrochemical stability of materials, boosts both electrical and lithium-ion conductivity, and also modulates the microstructure to form ultrathin multilayer nanosheets by rationally adjusting the feed ratio of HA. The resulting HA20-Mn-MOF (with a HA feed ratio of 20 %) demonstrates significant improvements in cycling stability and rate performance, with a reversible specific capacity of 1318.7mAh/g at 0.1 A/g after 100 cycles and a substantial capacity of 657.0mAh/g even after 1000 cycles at 1 A/g. An extraordinary V-shaped capacity reversal is observed for HA20-Mn-MOF during cycling. Ex-situ EPR (Electron Paramagnetic Resonance) investigation reveals this capacity growth is associated with the reoxidation of active manganese during cycling, in which a notable correlation between the specific capacity and the Mn2+ signal intensity in EPR spectra is found. These results suggest in-situ compositing HA with MOFs can be a costeffective strategy in regulating MOFs morphology and in achieving an optimized electrochemical performance for MOFs-based electrode materials in energy storage field.

Among the various transition metal oxides used in lithium-ion battery anodes, iron oxide (Fe2O3) has received extensive attention due to its low cost, good environmental compatibility and high theoretical capacity. However, the volume expansion and structural collapse during the charging-discharging cycling process significantly limited the practical application of Fe2O3. Herein, we demonstrate enhanced electrochemical properties and stability of Fe(2)O(3 )by anchoring it on metal-organic frameworks (MOFs). Through adjusting the MOF ligands and introducing humic acid (HA), we reached rational control of the morphology for the Fe2O3/MOF composites. The optimized sample, namely Fe2O3@HA-Fe-ATA, shows 3D cauliflower-like structure with abundant pores, which are beneficial to the active sites exposure, electrolyte penetration, as well as the tolerance toward volume expansion. Consequently, high reversible capacity of 1442.7 mAh g(- 1) (at 0.1 A g(- 1)), excellent rate performance (<11 % capacity decrease when current density increases from 0.1 A g(- 1) to 1 A g(- 1)), and satisfactory cycle stability (91 % capacity retention after 500 cycles at 1 A g(- 1)) are obtained. This work demonstrates that the rational design of MOF by introduction of appropriate ligand is a very efficient approach to optimize the electrochemical properties of the resultant electrode material.

Nowadays, metal-organic frameworks (MOFs) are regarded as promising anode materials for lithium-ion batteries (LIBs) due to their high porosity, tunable structure, and considerable surface area. However, limited by low conductivity and poor cycling stability, few MOF-based anodes can achieve stable cycling performance at high current densities for practical applications. Herein, we report the preparation of a unique interlocked smoothie-like anode material, named HA-Co-BPDC, for lithium-ion batteries through a facile two-step hydrothermal method. The as-prepared HA-Co-BPDC anode exhibits outstanding reversible capacity of 1603 mAh g(-1) at 0.1 A g(-1) and remains 971 mAh g(-1) at 1 A g(-1), exhibiting good rate capability. Most importantly, the HA-Co-BPDC anode shows excellent long-term cycling stability at ultra-high current density, due to the unique interlocked structure which endows high tolerance toward the volume expansion/contraction. Typically, specific capacities of 315 and 242 mAh g(-1) are obtained after 1000 cycles at 5 and 10 A g(-1), which delivers high capacity retention of 84% and 80%, respectively. Possessing outstanding reversible capacity, good rate capability, and excellent long-term cycling stability at ultra-high current density, the HA-Co-BPDC exhibits great potential in practical applications.

Ironoxide (Fe2O3) is emerging as a potentialanode alternative for lithium-ion batteries (LIBs) due to the meritsof high specific capacity, environmental friendliness, and cost-effectiveness.However, trapped by unsatisfactory cycling stability and rate capability,further modification is needed for Fe2O3 toachieve practical requirements. In this study, a Fe2O3-based composite anode (namely Fe2O3@HA-Fe-BPDC) with interlocked structure was designed and synthesizedfor pursuing enhanced electrochemical properties. Benefiting fromthe porous structure, abundant active sites, and good tolerance tovolume expansion, the as-prepared electrode exhibits significantlyboosted rate capability, excellent specific capacity, and satisfactoryreversibility. Typically, the Fe2O3@HA-Fe-BPDCanode provided an excellent specific capacity of 708 mAh g(-1) at 0.1 A g(-1) and remained at a high level of 332mAh g(-1) at 1 A g(-1), deliveringsignificantly improved rate performance than Fe2O3. Additionally, outstanding capacity retention (95.4%) was achievedat 1 A g(-1) after 600 charge/discharge cycles. Thestrategy based on the facile coprecipitation for fabricating Fe2O3 and MOF composite electrodes provides a feasibletechnique to develop a high-performance anode for LIBs.