Tin-nitrogen coordination boosted lithium-storage sites and electrochemical properties in covalent-organic framework with layer-assembled hollow structure.

Covalent-organic frameworks (COFs) and related composites show an enormous potential in next-generation high energy-density lithium-ion batteries. However, the strategy to design functional covalent organic framework materials with nanoscale structure and controllable morphology faces serious challenges. In this work, a layer-assembled hollow microspherical structure (Sn@COF-hollow) based on the tin-nitrogen (Sn-N) coordination interaction is designed. Such carefully-crafted hollow structure with large exposed surface area and metal center decoration endows the Sn@COF-hollow electrode with more activated lithium-reaction sites, including Sn ions, carbon-nitrogen double bond (CN) groups and carbon-carbon double bond (CC) units from aromatic benzene rings. Besides, the layer-assembled hollow structure of the Sn@COF-hollow electrode can also alleviate the volume expansion of electrode during repeated cycling, and achieve fast electrons/ions transmission and capacitance-dominated lithium-reaction kinetics, further leading to enhanced cycling performance and rate properties. In addition, the effective combination of the inorganic metal and organic framework components in the Sn@COF-hollow electrode can promote its improved conductivity and further enhance lithium-storage properties. Benefited from these merits, the Sn@COF-hollow electrode delivers highly reversible large capacities of 1080 mAh g-1 after 100 cycles at 100 mA g-1 and 685 mAh g-1 after 300 cycles at 1000 mA g-1. This work provides an interesting and effective way to design COF-based anodes of lithium-ion battery with improved electrochemical performances.

Functionalized Graphene Quantum Dots Modified Dioxin-Linked Covalent Organic Frameworks for Superior Lithium Storage.

Covalent organic framework, as an emerging porous nano-frame structure with pre-designed structure and custom properties, has been demonstrated as a prospective electrode for rechargeable Li-ion batteries. For improving the reversible capacity and long-term cycle stability of COF materials, we propose a GQDs modified COF material (COF-GQDs) and apply it as the anode for LIBs for the first time. This COF-GQDs electrode delivers enhanced long-term cycling performance with a large capacity of ∼820 mAh g-1 after 300 cycles at 100 mA g-1 and an improved rate performance. The enhanced lithium-storage performance, in terms of obvious-shortened activation process and high reversible capacities, can be attributed to the modification of carboxyl GQDs, which would activate more active sites (activated C=C groups from benzene rings) for lithium-storage, and provide fast lithium-ion transportation kinetic. Besides, the decreased interphase resistance, enhanced electronic conductivity, and prevented aggregation of needle-flake COF structure, originated from the addition of GQDs, which lead to the enhanced improved cycling stability of the COF-GQDs electrode. This manuscript can promote the further exploration on the design of COF-related materials with modification of functionalized carbonaceous materials to achieve enhanced lithium-storage properties for next-generation energy storage.

Imine-Induced Metal-Organic and Covalent Organic Coexisting Framework with Superior Li-Storage Properties and Activation Mechanism.

Due to the adjustable structure and the broad application prospects in energy and other fields, the exploration of porous organic materials [metal-organic polymers (MOPs), covalent organic frameworks (COFs), etc.] has attracted extensive attention. In this work, an imine-induced metal-organic and covalent organic coexisting framework (Co-MOP@COF) hybrid was designed based on the combination between the amino units from the organic ligands of Co-MOP and the aldehyde groups from COF. The obtained Co-MOP@COF hybrid with layer-decorated microsphere morphology exhibited good electrochemical cycling performance (a large reversible capacity of 1020 mAh g-1 after 150 cycles at 100 mA g-1 and a reversible capacity of 396 mAh g-1 at 500 mA g-1 ) as the anode for Li-ion batteries. The coexisting framework structure endowed the Co-MOP@COF hybrid with more surface area exposed in the exfoliated COF structure, which provided rapid Li-ion diffusion, better electrolyte infiltration, and effective activation of functional groups. Therefore, the Co-MOP@COF hybrid material achieved an enhanced Li storage mechanism involving multi-electron redox reactions, related to the CoII center and organic groups (C=C groups of benzene rings and C=N groups), and furthermore improved electrochemical performance.

Coordination-Induced Interlinked Covalent- and Metal-Organic-Framework Hybrids for Enhanced Lithium Storage.

Covalent organic frameworks (COF) or metal-organic frameworks have attracted significant attention for various applications due to their intriguing tunable micro/mesopores and composition/functionality control. Herein, a coordination-induced interlinked hybrid of imine-based covalent organic frameworks and Mn-based metal-organic frameworks (COF/Mn-MOF) based on the MnN bond is reported. The effective molecular-level coordination-induced compositing of COF and MOF endows the hybrid with unique flower-like microsphere morphology and superior lithium-storage performances that originate from activated Mn centers and the aromatic benzene ring. In addition, hollow or core-shell MnS trapped in N and S codoped carbon (MnS@NS-C-g and MnS@NS-C-l) are also derived from the COF/Mn-MOF hybrid and they exhibit good lithium-storage properties. The design strategy of COF-MOF hybrid can shed light on the promising hybridization on porous organic framework composites with molecular-level structural adjustment, nano/microsized morphology design, and property optimization.

Ultrafine ternary metal oxide particles with carbon nanotubes: a metal-organic-framework-based approach and superior lithium-storage performance.

Aiming to achieve metal-oxide-based electrodes for Li-ion batteries with enhanced energy density and cycling life, especially overcoming their negative volume expansion during cycling, more effort should be devoted to the exploration of the combination of morphology-controlled metal oxides with carbonaceous materials. In this work, we select dual/single-metallic organic frameworks immobilized on the surface of carbon nanotubes as the precursors to synthesize composites of ternary/single metal oxides with carbon nanotubes (ZnCo2O4@CNTs and ZnO@CNTs). The main product, ZnCo2O4@CNTs, consists of ultrafine ZnCo2O4 nanoparticles embedded deeply in the carbon nanotubes. The existence of small-size ternary metal oxides as well as the carbon nanotubes results in outstanding lithium-storage properties of the ZnCo2O4@CNT anode for lithium-ion batteries. It delivers an extremely high capacity (1507 mA h g-1, 100 mA g-1) after 200 cycles, which is larger than the theoretical value.