Polypyrrole-coated sodium manganate microspheres cathode for superior performance Sodium-ion batteries.

P2-Na0.67Mn0.67Ni0.33O2 is a promising cathode material for sodium ion batteries (SIBs) due to its low cost, high theoretical capacity, and non-toxicity. However, it still suffers from unsatisfactory cycling stability mainly incurred by the Jahn-Teller effect of Mn3+ and electrolyte decomposition on the electrode/electrolyte interface. Herein, the P2-Na0.67Ni0.33Mn0.67O2@PPy (NNMO@PPy) composite applied as cathode materials for SIBs is obtained by introducing conductive polypyrrole (PPy) as coating layer on the P2-Na0.67Ni0.33Mn0.67O2 (NNMO) microspheres. Numerous physical characterization methods indicate that the PPy layer was uniformly coated on the surface of NNMO microspheres without change in phase structure and morphology. The PPy coating layer can alleviate Mn dissolution and effectively suppress the side reactions between the electrolyte and electrode during cycling. The optimal NNMO@PPy-9 with 9 wt% PPy delivers a high capacity of 127.4 mAh/g at the current density at 150 mA g-1, an excellent cyclic stability with high capacity retention of 80.5 % after 300 cycles, and enhanced rate performance (169.3 mAh/g at 15 mA g-1 while 89.8 mAh/g at 600 mA g-1). Furthermore, hard carbon (-)//NNMO@PPy-9 (+) full cell delivers a high energy density of 305.1 Wh kg-1 and superior cycling stability with 88.2 % capacity retention after 150 cycles. In-situ X-ray diffraction experiment and electrochemical characterization verify the highly reversible structure evolution and robust P2-type phase structure of NNMO@PPy-9 for fast and stable Na+ diffusion. This effective strategy of using conductive PPy as a coating layer may provide a new insight to modify NNMO surface, improving the cycling stability and rate capability.

Sandwiched composite electrolyte with excellent interfacial contact for high-performance solid-state sodium-ion batteries.

Solid-state sodium-ion batteries have attracted significant attention due to their rich resources, high safety, and high energy density. However, the lower ionic conductivity and inferior interfacial contact between solid-state electrolytes (SSEs) and electrodes limit their practical applications. Herein, polyvinylideneuoride-co-hexauoropropylene (PVDF-HFP) membrane is selected and a novel sandwiched composite PVDF-HFP/Na2.5Zr1.95Ce0.05Si2.2P0.8O11.3F0.7/PVDF-HFP (G-NZC0.05SPF0.7-G) SSEs is well designed. The ionic conductivity of Na3Zr2Si2PO12 is enhanced by Ce4+/F- co-doping. The effects of Ce4+ and F- doping on the crystal structure, density, and ionic conductivity for Na3Zr2Si2PO12 are well investigated. The optimal NZC0.05SPF0.7 delivers a high ionic conductivity of 1.39 × 10-3 S cm-1 at 25 â„ƒ. Moreover, the PVDF-HFP membrane can significantly enhance the interface compatibility between NZC0.05SPF0.7 and electrodes. The as-prepared G-NZC0.05SPF0.7-G exhibits a large ionic conductivity of 1.07 × 10-3 S cm-1 at 25 â„ƒ, wide electrochemical stability window up to 4.5 V, high critical current density of 1.2 A cm-2, and stable Na plating/stripping over 600 h at 0.3 A cm-2. The solid-state Na0.67Mn0.47Ni0.33Ti0.2O2/G-NZC0.05SPF0.7-G/Na battery delivers a remarkable cycling stability and rate capability at 25 â„ƒ, indicating that the as-prepared G-NZC0.05SPF0.7-G has a promising application for solid-state SIBs. This study demonstrates an effective strategy to develop advanced solid-state electrolytes for solid-state SIBs.

Construction of a Few-Layered COF@CNT Composite as an Ultrahigh Rate Cathode for Low-Cost K-Ion Batteries.

Potassium-ion batteries (PIBs) are attracting great interest for large-scale energy storage owing to the abundant resources and low redox potential of K+/K. However, the large volume changes and slow kinetics caused by the larger ionic radius of K+ for cathode materials remain a critical challenge for PIBs. Herein, we construct few-layered covalent organic frameworks integrated with carboxylated carbon nanotubes (DAAQ-COF@CNT) as cathode materials for PIBs. The synthesized DAAQ-COF@CNT features numerous active sites, a stable conductive framework, and an appropriate surface area with nanopores, which can render high electrical conductivity, shorten the ion/electron diffusion distance, and accelerate K+ diffusion. In consequence, the DAAQ-COF@CNT delivers a high reversible capacity of 157.7 mAh g-1 at 0.1 A g-1, an excellent rate capability of 111.2 mAh g-1 at 1 A g-1, and a long cycling stability of 77.6% capacity retention after 500 cycles at 0.5 A g-1. The integrated characterization of ex situ X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and theoretical simulation discloses that the storage mechanism of DAAQ-COF@CNT is based on the reversible reaction between electroactive C═O groups and K+ during two successive steps. This work provides a promising high-performance cathode material for PIBs and encourages the development of new types of covalent organic frameworks for PIBs.

Facile Assembly of Large-Area 2D Microgel Colloidal Crystals Using Charge-Reversible Substrates.

2D colloidal crystals (CCs) have important applications; however, the fabrication of large-area, high-quality 2D CCs is still far from being trivial, and the fabrication of 2D microgel CCs is even harder. Here, we have demonstrated that they can be facilely fabricated using charge-reversible substrates. The charge-reversible substrates were prepared by modification with amino groups. The amino groups were then protected by amidation with 2,2-dimethylsuccinic anhydride. At acidic pH, the surface charge of the modified substrate will change from negative to positive as a result of the hydrolysis of the amide bonds and the regeneration of the amino groups. 2D microgel CCs can be simply fabricated by applying a concentrated microgel dispersion on the modified substrate. The negatively charged surface of the substrate allows the negatively charged microgel spheres, especially those close to the substrate, to self-assemble into 3D CCs. With the gradual hydrolysis of the amide bonds and the charge reversal of the substrate, the first 111 plane of the 3D assembly is fixed in situ on the substrate. The resulting 2D CC has a high degree of ordering because of the high quality of the parent 3D microgel CC. Because large-area 3D microgel CCs can be facilely fabricated, this method allows for the fabrication of 2D CCs of any size. Nonplanar substrates can also be used. In addition, the interparticle distance of the 2D array can be tuned by the concentration of the microgel dispersion. Besides rigid substrates (such as glass slides, quartz slides, and silicon wafers), flexible polymer films, including polyethylene terephthalate and poly(vinyl chloride) films, were also successfully used as substrates for the fabrication of 2D microgel CCs.

Fabrication of Large-Area Two-Dimensional Microgel Colloidal Crystals via Interfacial Thiol-Ene Click Reaction.

A method for the fabrication of high quality, large area 2D colloidal crystals (CCs) using poly(N-isopropylacrylamide) (PNIPAM) microgel sphere, an extremely soft colloid, as building block was proposed. First the microgel spheres were assembled into 3D colloidal crystals. The first 111 plane of the 3D crystal close to the substrate was then fixed in situ onto the substrate. Highly efficient photoinitiated thiol-ene coupling was chosen for the fixing purpose. Thanks to the high quality of 3D microgel CCs, the resulting 2D CCs exhibit a high degree of ordering. Large area 2D CCs were fabricated because large area 3D microgel CCs can be facilely fabricated. Besides planar substrates, the method allows the fabrication of 2D CCs on curved surface, too. In addition, the interpartical distance in the 2D CCs can be tuned by the concentration of the microgel dispersion.