Ion Co-storage in Porous Organic Frameworks through On-site Coulomb Interactions for High Energy and Power Density Batteries.

Fast and continuous ion insertion is blocked in the common electrodes operating with widely accepted single-ion storage mechanism, primarily due to Coulomb repulsion between the same ions. It results in an irreconcilable conflict between capacity and rate performance. Herein, we designed a porous organic framework with novel multiple-ion co-storage modes, including PF6 - /Li+ , OTF- /Mg2+ , and OTF- /Zn2+ co-storage. The Coulomb interactions between cationic and anionic carriers in the framework can significantly promote electrode kinetics, by rejuvenating fast ion carrier migration toward framework interior. Consequently, the framework via PF6 - /Li+ co-storage mode shows a high energy density of 878 Wh kg-1 cycled more than 20 000 cycles, with an excellent power density of 28 kW kg-1 that is already comparable to commercial supercapacitors. The both greatly improved energy and power densities via the co-storage mode may pave a way for exploring new electrodes that are not available from common single-ion electrodes.

Localized Ligands Assist Ultrafast Multivalent-Cation Intercalation Pseudocapacitance.

Rechargeable batteries based on multivalent cation (Mvn+ , n>1) carriers are considered potentially low-cost alternatives to lithium-ion batteries. However, the high charge-density Mvn+ carriers generally lead to sluggish kinetics and poor structural stability in cathode materials. Herein, we report an Mvn+ storage via intercalation pseudocapacitance mechanism in a 2D bivalve-like organic framework featured with localized ligands. By switching from conventional intercalation to localized ligand-assisted-intercalation pseudocapacitance, the organic cathode exhibits unprecedented fast kinetics with little structural change upon intercalation. It thus enables an excellent power density of 57 kW kg-1 over 20000 cycles for Ca2+ storage and a power density of 14 kW kg-1 with a long cycling life over 45000 cycles for Zn2+ storage. This work may provide a largely unexploited route toward constructing a local dynamic coordination microstructure for ultrafast Mvn+ storage.

Engineering Mesoporous Single Crystals Co-Doped Fe2O3 for High-Performance Lithium Ion Batteries.

To achieve high-efficiency lithium ion batteries (LIBs), an effective active electrode material is vital. For the first time, mesoporous single crystals cobalt-doped Fe2O3 (MSCs Co-Fe2O3) is synthesized using formamide as a pore forming agent, through a solvothermal process followed by calcination. Compared with mesoporous single crystals Fe2O3 (MSCs Fe2O3) and cobalt-doped Fe2O3 (Co-Fe2O3), MSCs Co-Fe2O3 exhibits a significantly improved electrochemical performance with high reversible capacity, excellent rate capability, and cycling life as anode materials for LIBs. The superior performance of MSCs Co-Fe2O3 can be ascribed to the combined structure characteristics, including Co-doping and mesoporous single-crystals structure, which endow Fe2O3 with rapid Li+ diffusion rate and tolerance for volume change.

Robust dual-cross-linked networks enable stable silicon anodes.

The simultaneous attainment of long cycle life and high energy in Si anodes remains challenging. Herein, we introduce the concept of primary building units as organizing units to construct durable and conductive electrode architectures, which helps to facilitate the coalescence of Si nanoparticles with conductive pathways and prevent nanoparticle aggregation.

Enhancing Co/Co2VO4 Li-ion battery anode performances via 2D-2D heterostructure engineering.

High-capacity Co2VO4 has become a potential anode material for lithium-ion batteries (LIBs), benefiting from its lower output voltage during cycling than other cobalt vanadates. However, the application of this new conversion-type electrode is still hampered by its inherent large volume variation and poor kinetics. Here, a 2D-2D heterostructure building strategy has been developed to enhance the electrode performance of Co2VO4 through construction of Co/Co2VO4 nanocomposites converted from the in situ phase separation of Co2V2O7·3.3H2O nanosheets. Co/Co2VO4 based on face-to-face contact exhibits the optimized stacking configuration, where Co nanocrystals give gaps of several nanometers between stacked Co2VO4 nanosheets, enabling full contact with the electrolyte, a shorter transport path of lithium ions and more reactive sites. With this design, Co/Co2VO4 anodes deliver outstanding reversible capacity (750 mA h g-1 at 1 A g-1) with ultrahigh capacity retention rate, and excellent cycle stability at high rate (520 mA h g-1 at 5 A g-1 retained after 400 cycles). An "active center's charge transfer-capacity compensation" model was proposed based on capacity analysis, XPS depth analysis and HRTEM observation to uncover the fundamental reason of the excellent cycle performance. This in situ 2D-2D heterostructure constructing strategy may open up the possibility for designing high-performance LIBs.

Metal-organic framework derived amorphous VOx coated Fe3O4/C hierarchical nanospindle as anode material for superior lithium-ion batteries.

Lithium-ion batteries (LIBs) are widely regarded as a promising electrochemical energy storage device, due to their high energy density and good cycling stability. To date, the development of anode materials for LIBs is still confronted with many serious problems, and much effort is required for constructing more ideal anode materials. Herein, starting with metal-organic frameworks (MOFs), an amorphous VOx coated Fe3O4/C hierarchical nanospindle has been successfully synthesized. The obtained Fe3O4/C@VOx nanospindle has a uniform particle size of ∼100 nm in diameter and ∼400 nm in length and consists of ultrafine Fe3O4 nanoparticles (∼5 nm) embedded in a porous carbon matrix as the core and an amorphous VOx layer as the shell. Notably, as the anode material for LIBs, Fe3O4/C@VOx delivers a high coulombic efficiency (74.2%) and a large capacity of 845 mA h g-1 after 500 cycles at 1000 mA g-1. A prominent discharge reversible capacity of 340 mA h g-1 is also still retained at 5000 mA g-1. More importantly, the presented facile MOF-derived route could be easily extended to other functional materials for widespread applications.