Nanostructured Ni/Ti_3C_2T_x MXene hybrid as cathode for lithium-oxygen battery

Ti_3C_2 belongs to MXenes family,which is a new two-dimensional material and has been applied in many fields.With simple method of hydrothermal and high temperature calcination,nano structured Ni/Ti_3C_2T_x hybrid was synthesized.The stable layer structure of Ti_3C_2 MXene providing high surface area as well as excellent electronic conductivity are beneficial for deposition and decomposition of discharge product Li_2O_2.Furthermore,possessing special catalytic activity,Ni nanoparticles with size of about 20 nm could accelerate Li_2O_2 breaking down.Taking advantage of two kinds of materials,Ni/Ti_3C_2T_x hybrid as cathode of Li-O_2 battery can achieve a maximal specific capacity of 20,264 mAh/g in 100 mA/g and 10,699 mAh/g in 500 mA/g at the first cycle.This work confirms that the prepared Ni/Ti_3C_2T_x hybrid exhibiting better cycling stability points out a new guideline to improve the electrochemical performance of lithium-oxygen batteries.     

富锂掺杂Li1.06Co0.05Cr0.1Mn1.85O4的合成及电化学性能研究

锂离子电池具有比能量高、功率大、使用寿命长、无记忆效应、性能价格比高等优点,从而成为可充式电源的主要选择对象.锰由于资源丰富、价廉、环境友好等优点,使锰酸锂(LiMn2O4)成为最有希望取代钴酸锂的正极材料.但锰酸锂的放电容量相对较低,结构欠稳定,容量衰减严重,作为正极材料还无法与钴酸锂相比,近年来做了大量的研究工作以改善它的电化学性能[1～6].最近Youngjoon Shin等研究发现[7]用少量的Li与Ni共同替代LiMn2O4中的Mn得到的LiMn2-2yLiyNiyO4的电化学性能要优于单元素替代的LiMn2-xMxO4(M=Li,Cr,Fe,Co,Ni)的电化学性能.     

锂离子电池正极材料LiMn2O4的低热固相合成与性能表征

锂离子电池具有比能量高、环境污染小等优点,广泛应用于手提电话、便携式电脑、摄像机等设备中。其正极材料的研究是锂离子电池的研究重点。层状结构的LiCoO2、LiNiO2和尖晶石结构的LiMn2O4是仅有的三种能在3.5V以上电位可嵌入Li的正极材料[1~3]。目前市售的锂离子电池主要采用LiCoO2作正极材料,但由于Co资源缺乏和价格相对昂贵,而锰资源丰富,价格低廉且无毒,对环境友好,因此世界各国都在大力进行以LiMn2O4为正极材料的锂离子电池的实用化研究。LiMn2O4传统的制备方法是高温固相反应合成法[4~7],但由于Mn的变价多,与Li形成贫Li或…     

MnO2上氧气第一个电子转移步骤的从头计算研究

采用裸露簇和嵌入簇模型, 对β-MnO₂ (001), (110), (111)三个晶面以及O₂在(110)晶面的单址吸附模式(Pauling和Griffths模式), 进行从头计算. 从β-MnO₂ (001), (110), (111)三个晶面的电子结构差异以及O₂在(110)晶面吸附的吸附能、几何结构、集居数以及净电荷数分析得到: (001), (110), (111)三个晶面中(110)晶面的催化活性最高, 其活性顺序为(110)＞(111)＞(001). 氧气在(110)晶面的吸附, Pauling和Griffths两种吸附模式均存在, 属于化学吸附中的离子吸附. 氧气与MnO₂固体间发生了单电子转移, 氧气得到电子被还原成O₂^-, 转移电子属于整个体系, 具有离域性.     

Phosphoryl‐Rich Flame‐Retardant Ions (FRIONs): Towards Safer Lithium‐Ion Batteries

The functionalized catecholate, tetraethyl (2,3‐dihydroxy‐1,4‐phenylene)bis(phosphonate) (H₂‐DPC), has been used to prepare a series of lithium salts Li[B(DPC)(oxalato)], Li[B(DPC)₂], Li[B(DPC)F₂], and Li[P(DPC)₃]. The phosphoryl‐rich character of these anions was designed to impart flame‐retardant properties for their use as potential flame‐retardant ions (FRIONs), additives, or replacements for other lithium salts for safer lithium‐ion batteries. The new materials were fully characterized, and the single‐crystal structures of Li[B(DPC)(oxalato)] and Li[P(DPC)₃] have been determined. Thermogravimetric analysis of the four lithium salts show that they are thermally stable up to around 200 °C. Pyrolysis combustion flow calorimetry reveals that these salts produce high char yields upon combustion.     

Electrostatic Interactions Leading to Hierarchical Interpenetrating Electroconductive Networks in Silicon Anodes for Fast Lithium Storage

Recently, the frequency of combining MXene, which has unique properties such as metal-level conductivity and large specific surface area, with silicon to achieve excellent electrochemical performance has increased considerably. There is no doubt that the introduction of MXene can improve the conductivity of silicon and the cycling stability of electrodes after elaborate structure design. However, most exhaustive contacts can only improve the electrode conductivity on the plane. Herein, a MXene@Si/CNTs (HIEN-MSC) composite with hierarchical interpenetrating electroconductive networks has been synthesized by electrostatic self-assembly. In this process, the CNTs are first combined with silicon nanoparticles and then assembled with MXene nanosheets. Inserting CNTs into silicon nanoparticles can not only reduce the latter‘s agglomeration, but also immobilizes them on the three-dimensional conductive framework composed of CNTs and MXene nanosheets. Therefore, the HIEN-MSC electrode shows superior rate performance (high reversible capacity of 280 mA h⁻¹ even tested at 10 A g⁻¹), cycling stability (stable reversible capacity of 547 mA h g⁻¹ after 200 cycles at 1 A g⁻¹) and applicability (a high reversible capacity of 101 mA h g⁻¹ after 50 cycles when assembled with NCM622 into a full cell). These results may provide new insights for other electrodes with excellent rate performance and long-cycle stability.     

The Efficient K Ion Storage of M2P2O7/C (M=Fe,Co, Ni) Anode Derived from Organic-Inorganic Phosphate Precursors

Metal phosphates have been widely explored in lithium ion batteries and sodium ion batteries owing to high theoretical capacities, mild toxicity and low cost. However, their potassium ion battery applications are less reported due to the limited conductivity and the slow diffusion kinetics. Considering these drawbacks, novel structured M₂P₂O₇/C (M=Fe, Co, Ni) nanoflake composites are prepared through an organic-phosphors precursor-assisted solvothermal method and a subsequent high temperature annealing process. The designed Co₂P₂O₇/C composite exhibits the highest rate capacity with 502 mAh g⁻¹ at 0.1 A g⁻¹ and good cyclability for 900 cycles at 1 A g⁻¹ and 2 A g⁻¹ when compared with Ni and Fe based composites. The superior electrochemical performance can be attributed to their unique nanoparticle-assembled nanoflake structure, which can afford enough active sites for K⁺ intercalation. In addition, the robust pyrophosphate crystal structure and the in situ formed carbon composition also have positive effects on enhancing the long-term cycling performance and the electrode's conductivity. Finally, this organic-phosphors precursor induced simple approach can be applied for easy fabrication of other pyrophosphate/carbon hybrids as advanced electrodes.     

Tunable and Specific Formation of C@NiCoP Peapods with Enhanced HER Activity and Lithium Storage Performance

The superior properties of nanomaterials with a special structure can provide prospects for highly efficient water splitting and lithium storage. Herein, we fabricated a series of peapodlike C@Ni_2?xCo_xP (x≤1) nanocomposites by an anion‐exchange pathway. The experimental results indicated that the HER activity of C@Ni_2?xCo_xP catalyst is strongly related to the Co/Ni ratio, and the C@NiCoP got the highest HER activity with low onset potential of ～45 mV, small Tafel slope of ～43 mV dec^?1, large exchange current density of 0.21 mA cm^?2, and high long‐term durability (60 h) in 0.5 m H₂SO₄ solutions. Equally importantly, as an anode electrode for lithium batteries, this peapodlike C@NiCoP nanocomposite gives excellent charge–discharge properties (e.g., specific capacity of 670 mAh g^?1 at 0.2 A g^?1 after 350 cycles, and a reversible capacity of 405 mAh g^?1 at a high current rate of 10 A g^?1). The outstanding performance of C@NiCoP in HER and LIBs could be attributed to the synergistic effect of the rational design of peapodlike nanostructures and the introduction of Co element.