Rational Design of Hierarchically Open‐Porous Spherical Hybrid Architectures for Lithium‐Ion Batteries

Controlling the internal microstructure and overall morphology of building blocks used to form hybrid materials is crucial for the realization of deterministically designed architectures with desirable properties. Here, integrative spray‐frozen (SF) assembly is demonstrated for forming hierarchically structured open‐porous microspheres (hpMSs) composed of Fe₃O₄ and reduced graphene oxide (rGO). The SF process drives the formation of a radially aligned microstructure within the sprayed colloidal droplets and also controls the overall microsphere morphology. The spherical Fe₃O₄/rGO hpMSs contain interconnected open pores, which, when used as a lithium‐ion battery anode, enables them to provide gravimetric and volumetric capacities of 1069.7 mAh g^?1 and 686.7 mAh cm^?3, much greater than those of samples with similar composition and different morphologies. The hpMSs have good rate and cycling performance, retaining 78.5% capacity from 100 to 1000 mA g^?1 and 74.6% capacity over 300 cycles. Using in situ synchrotron X‐ray absorption spectroscopy, the reaction pathway and phase evolution of the hpMSs are monitored enabling observation of the very small domain size and highly disordered nature of Fe_xO_y. The reduced capacity fade relative to other conversion systems is due to the good electrical contact between the pulverized Fe_xO_y particles and rGO, the overall structural integrity of the hpMSs, and the interconnected open porosity.     

Sulfur‐Impregnated,Sandwich‐Type,Hybrid Carbon Nanosheets with Hierarchical Porous Structure for High‐Performance Lithium‐Sulfur Batteries

Sandwich‐type hybrid carbon nanosheets (SCNMM) consisting of graphene and micro/mesoporous carbon layer are fabricated via a double template method using graphene oxide as the shape‐directing agent and SiO₂ nanoparticles as the mesoporous guide. The polypyrrole synthesized in situ on the graphene oxide sheets is used as a carbon precursor. The micro/mesoporous strcutures of the SCNMM are created by a carbonization process followed by HF solution etching and KOH treatment. Sulfur is impregnated into the hybrid carbon nanosheets to generate S@SCNMM composites for the cathode materials in Li‐S secondary batteries. The microstructures and electrochemical performance of the as‐prepared samples are investigated in detail. The hybrid carbon nanosheets, which have a thickness of about 10–25 nm, high surface area of 1588 m² g^?1, and broad pore size distribution of 0.8–6.0 nm, are highly interconnected to form a 3D hierarchical structure. The S@SCNMM sample with the sulfur content of 74 wt% exhibits excellent electrochemical performance, including large reversible capacity, good cycling stability and coulombic efficiency, and good rate capability, which is believed to be due to the structure of hybrid carbon materials with hierarchical porous structure, which have large specific surface area and pore volume.     

In Situ TEM Study of Volume Expansion in Porous Carbon Nanofiber/Sulfur Cathodes with Exceptional High‐Rate Performance

Although lithium sulfur batteries (LSBs) have attracted much interest owing to their high energy densities, synthesis of high‐rate cathodes and understanding their volume expansion behavior still remain challenging. Herein, electrospinning is used to prepare porous carbon nanofiber (PCNF) hosts, where both the pore volume and surface area are tailored by optimizing the sacrificial agent content and the activation temperature. Benefiting from the ameliorating functional features of high electrical conductivity, large pore volume, and Li ion permselective micropores, the PCNF/A550/S electrode activated at 550 °C exhibits a high sulfur loading of 71 wt%, a high capacity of 945 mA h g^?1 at 1 C, and excellent high‐rate capability. The in situ transmission electron microscope examination reveals that the lithiation product, Li₂S, is contained within the electrode with only ≈35% volume expansion and the carbon host remains intact without fracture. In contrast, the PCNF/A750/S electrode with damaged carbon spheres exhibits sulfur sublimation, a larger volume expansion of over 61%, and overflowing of Li₂S, a testament to its poor cyclic stability. These findings provide, for the first time, a new insight into the correlation between volume expansion and electrochemical performance of the electrode, offering a potential design strategy to synthesize high‐rate and stable LSB cathodes.     

3D Porous Cu–Zn Alloys as Alternative Anode Materials for Li‐Ion Batteries with Superior Low T Performance

Zinc is recently gaining interest in the battery community as potential alternative anode material, because of its large natural abundance and potentially larger volumetric density than graphite. Nevertheless, pure Zn anodes have shown so far very poor cycling performance. Here, the electrochemical performance of Zn‐rich porous Cu–Zn alloys electrodeposited by an environmentally friendly (aqueous) dynamic hydrogen bubble template method is reported. The lithiation/delithiation mechanism is studied in detail by both in situ and ex situ X‐ray diffraction, indicating the reversible displacement of Zn from the Cu–Zn alloy upon reaction with Li. The influence of the alloy composition on the performance of carbon‐ and binder‐free electrodes is also investigated. The optimal Cu:Zn atomic ratio is found to be 18:82, which provides impressive rate capability up to 10 A g^?1 (≈30C), and promising capacity retention upon more than 500 cycles. The high electronic conductivity provided by Cu, and the porous electrode morphology also enable superior lithium storage capability at low temperature. Cu₁₈Zn₈₂ can indeed steadily deliver ≈200 mAh g^?1 at ?20 °C, whereas an analogous commercial graphite electrode rapidly fades to only 12 mAh g^?1.     

A 3D Lithium/Carbon Fiber Anode with Sustained Electrolyte Contact for Solid‐State Batteries

To reconcile the energy storage ability and operational safety of lithium metal batteries (LMBs), a transformation from a liquid to a solid‐state system is required. However, Li volume variation, poor interfacial contact, and high operation temperatures hinder its practical applications. To address the above issues, here, an integral structure design for solid‐state LMBs is shown, in which a Li‐preinfused 3D carbon fiber (Li/CF) anode is ionically connected to a cathode via an autopolymerized gel electrolyte. The gel electrolyte helps to encapsulate the liquid electrolyte within the Li/CF anode and the cathode to improve the interfacial contact. The gel also serves as a reservoir that balances the liquid electrolyte supply during repeated Li stripping/plating process. As a result, the symmetrical cells and full cells with Li/CF electrodes exhibit improved cycling stability and effective suppression of dendrites at ambient temperature. This work facilitates the realization of solid‐state LMBs with high energy and high safety.