Sodium-ion batteries are promising alternatives to lithium-ion batteries for large-scale applications. However, the low capacity and poor rate capability of existing anodes for sodium-ion batteries are bottlenecks for future developments. Here, we report a high performance nanostructured anode material for sodium-ion batteries that is fabricated by high energy ball milling to form black phosphorus/Ketjenblack-multiwalled carbon nanotubes (BPC) composite. With this strategy, the BPC composite with a high phosphorus content (70 wt %) could deliver a very high initial Coulombic efficiency (>90%) and high specific capacity with excellent cyclability at high rate of charge/discharge (∼1700 mAh g(-1) after 100 cycles at 1.3 A g(-1) based on the mass of P). In situ electrochemical impedance spectroscopy, synchrotron high energy X-ray diffraction, ex situ small/wide-angle X-ray scattering, high resolution transmission electronic microscopy, and nuclear magnetic resonance were further used to unravel its superior sodium storage performance. The scientific findings gained in this work are expected to serve as a guide for future design on high performance anode material for sodium-ion batteries.
The corrosion of aluminum current collectors and the oxidation of solvents at a relatively high potential have been widely investigated with an aim to stabilize the electrochemical performance of lithium-ion batteries using such components. The corrosion behavior of aluminum current collectors was revisited using a home-build high-precision electrochemical measurement system, and the impact of electrolyte components and the surface protection layer on aluminum foil was systematically studied. The electrochemical results showed that the corrosion of aluminum foil was triggered by the electrochemical oxidation of solvent molecules, like ethylene carbonate, at a relative high potential. The organic radical cations generated from the electrochemical oxidation are energetically unstable and readily undergo a deprotonation reaction that generates protons and promotes the dissolution of Al from the aluminum foil. This new reaction mechanism can also shed light on the dissolution of transitional metal at high potentials.
In contrast to the stable cycle performance of space confined Se-based cathodes for lithium batteries in carbonate-based electrolytes, their common capacity fading in ether-based electrolytes has been paid less attention and not yet well-addressed so far. In this work, the lithiation/delithiation of amorphous Se2S5 confined in micro/mesoporous carbon (Se2S5/MPC) cathode was investigated by in situ X-ray near edge absorption spectroscopy (XANES) and theoretical calculations. The Se2S5/MPC composite was synthesized by a modified vaporization-condensation method to ensure a good encapsulation of Se2S5 into the pores of MPC host. In situ XANES results illustrated that the lithiation/delithiation reversibility of Se component was gradually decreased in ether-based electrolytes, leading to an aggravated formation of long-chain polyselenides during cycling and further capacity decay. Moreover, ab initio calculations revealed that the binding energy of polyselenides (Li2Sen) with carbon host is in an order of Li2Se6 > Li2Se4 > Li2Se. The insights into the failure mechanism of Se-based cathode gain in this work are expected to serve as a guide for future design on high performance Se-based cathodes.
ZnO/C hierarchical porous nanorods were synthesized through one-pot wet-chemical reaction followed by thermal calcination. It was found that ZnO/C porous nanorods are composed of numerous nanograins, exhibiting a hierarchical micro/nanostructure.In-situ synchrotron high energy X-ray diffraction study revealed that ZnO/C hierarchical porous nanorods involve a two-step reversible lithiation mechanism during charge/discharge; and part of ZnO and Zn remain at the end of the first discharge and charge process, respectively, leading to a low coulombic efficiency in the initial few cycles. The electrochemical test demonstrated that the reversible capacity and the rate performance of ZnO/C hierarchical porous nanorods anode have been greatly improved by PEDOT-PSS coating, which could maintain a reversible capacity of 623.94 mAh g -1 after 1500 cycles at 1 C. Its excellent high rate capability and long cycle stability were attributed to the high electronic conductivity of PEDOT-PSS coating layer and the hierarchical structures of ZnO/C porous nanorods.
Room-temperature sodium-ion batteries have attracted increased attention for energy storage due to the natural abundance of sodium. However, it remains a huge challenge to develop versatile electrode materials with favorable properties, which requires smart structure design and good mechanistic understanding. Herein, we reported a general and scalable approach to synthesize three-dimensional (3D) titania-graphene hybrid via electrostatic-interaction-induced self-assembly. Synchrotron X-ray probe, transmission electron microscopy, and computational modeling revealed that the strong interaction between titania and graphene through comparably strong van der Waals forces not only facilitates bulk Na intercalation but also enhances the interfacial sodium storage. As a result, the titania-graphene hybrid exhibits exceptional long-term cycle stability up to 5000 cycles, and ultrahigh rate capability up to 20 C for sodium storage. Furthermore, density function theory calculation indicated that the interfacial Li, K, Mg and Al storage can be enhanced as well. The proposed general strategy opens up new avenues to create versatile materials for advanced battery systems.
Sodium-ion batteries (SIBs) have been considered as one of the promising power source candidates for the stationary storage industries owing to the much lower cost of sodium than lithium. It is well-known that the electrode materials largely determine the energy density of the battery systems. However, recent discoveries on the electrode materials showed that most of them present distinct lithium and sodium storage performance, which is not yet well understood. In this work, we performed a comparative understanding on the structural changes of porous cobalt oxide during its electrochemical lithiation and sodiation process by in operando synchrotron small angel X-ray scattering, X-ray diffraction, and X-ray absorption spectroscopy. It was found that compared to the lithiation process, the porous cobalt oxide undergoes less pore structure changes, oxidation state, and local structure changes as well as crystal structure evolution during its sodiation process, which is attributed to the intrinsic low sodiation activity of cobalt oxide as evidenced by ab initio molecular dynamics simulations. Moreover, it was indicated that the sodiation activity of metal sulfides is higher than that of metal oxides, indicating a better candidate for SIBs. Such understanding is crucial for future design and improvement of high-performance electrode materials for SIBs.
In situ high energy X-ray diffraction (HEXRD) and in situ X-ray absorption near edge spectroscopy (XANES) were carried out to understand the soild state synthesis of Na x MnO 2 , with particular interest on the synthesis of P2 type Na 2/3 MnO 2. It was found that there were multi intermediate phases formed before NaMnO 2 appeared at about 600 o C. And the final product after cooling process is a combination of O'3 NaMnO 2 with P2 Na 2/3 MnO 2. A P2 type Na 2/3 MnO 2 was synthesized at reduced temperature (600 o C). The influence of Na 2 CO 3 impurity on the electrochemical performance of P2 Na 2/3 MnO 2 was thoroughly investigated in our work. It was found that the content of Na 2 CO 3 can be reduced by optimizing Na 2 CO 3 /MnCO 3 ratio during the solid state reaction or other post treatment such as washing with water. We expected our results could provide a good guide for future development of high performance cathode materials for sodium-ion batteries.
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