可充电镁电池负极改性策略

可充电镁电池具有理论体积比容量大、 地壳丰度高、 成本低、 环境友好及更为安全等优点, 是未来高能量存储系统发展的重要方向之一. 在大多数传统电解液中, 镁金属负极表面形成的钝化膜会阻碍镁的可逆沉积溶解过程, 从而限制了可充电镁电池的商业化应用. 由于存在成本高、 合成步骤复杂、 离子电导率低及难以同时与正负极兼容等问题, 聚焦于解决镁负级钝化问题的电解液研究陷入瓶颈. 因此, 通过对镁电池负极进行修饰改性, 使其在传统电解液中实现可逆过程是一种具有发展前景的策略. 本文从合金负极及人工界面形成两方面总结了近年来用于可充电镁电池负极改性的策略, 并在分析对比的基础上提出了进一步发展的结论和展望.     

A polythiophene derivative bearing TEMPO as a cathode material for rechargeable batteries

A polythiophene derivative bearing TEMPO radical was synthesized by oxidative chemical polymerization of its monomer. The polymer had a high spin density (2.05 × 10²¹ spins/g of polymer). CV studies of the polymer showed that the electrochemical redox reaction of the TEMPO radicals were completely reversible. We demonstrated, for the first time, construction and charge/discharge characteristics of an organic radical battery utilizing a TEMPO bearing polythiophene based cathode material. The battery had an initial specific discharge capacity of 79 A h/kg (87% of the theoretical capacity) and an average output voltage of 3.6 V. The specific energy capacity initially discharged was 268 W h/kg.     

MWNT/C/Mg1.03Mn0.97SiO4 hierarchical nanostructure for superior reversible magnesium ion storage

We first design and synthesize a MWNT/C/Mg_1.03Mn_0.97SiO₄ hierarchical nanostructure composed of MWNTs pinning the surface of the Mg_1.03Mn_0.97SiO₄ nanoparticles, with simultaneous tethering to Mg_1.03Mn_0.97SiO₄ particles via an interfacial amorphous carbon phase bonding, through a facile CVD method. It is further demonstrated that the nanocomposite exhibits a reversible capacity as high as 300 mAh g⁻¹ at 0.2 C and a stable cycling performance at 0.5 C when utilized as a cathode material for rechargeable magnesium batteries.     

正极集流体对可充镁电池电化学性能的影响

以目前常用的Chevrel相Mo₆S₈作为正极材料, 涂覆在不同集流体(不锈钢、镍、铜、钛) 上, 以镁为负极,研究了在(PhMgCl)₂-AlCl₃/四氢呋喃(简称THF)“二代”电解液中集流体对可充镁电池电化学性能的影响. 恒流放电-充电结果显示在不锈钢集流体上电池电压极化最小, 并且具有较好的循环稳定性; 镍、铜次之; 钛集流体上的极化最大, 循环稳定性也最差. 并通过对比放电-充电循环前后电极和集流体表面的微观结构, 探讨了集流体对电池性能显著影响的原因. 电解液对集流体会造成腐蚀, 不同集流体在电解液中的稳定性有差异; 正极材料涂覆在不同集流体上, 电极表面状况有差异; 负载活性材料后集流体发生腐蚀的电位有所降低, 使集流体更易受到电解液的腐蚀.     

Amphoteric Cellulose-Based Double-Network Hydrogel Electrolyte Toward Ultra-Stable Zn Anode

Zinc (Zn) metal anode suffers from uncontrollable Zn dendrites and parasitic side reactions at the interface, which restrict the practical application of aqueous rechargeable zinc batteries (ARZBs). Herein, an amphoteric cellulose-based double-network is introduced as hydrogel electrolyte to overcome these obstacles. On one hand, the amphoteric groups build anion/cation transport channels to regulate electro-deposition behavior on Zn (002) crystal plane enabled by homogenizing Zn²⁺ ions flux. On the other hand, the strong bonding between negatively charged carboxyl groups and Zn²⁺ ions promote the desolvation process of [Zn(H₂O)₆]²⁺ to eliminate side reactions. Based on the above two functions, the hydrogel electrolyte enables an ultra-stable cycling with a cumulative capacity of 7 Ah cm⁻² at 20 mA cm⁻²/20 mAh cm⁻² for Zn||Zn cell. This work provides significant concepts for developing hydrogel electrolytes to realize stable anode for high-performance ARZBs.     

可充镁电池有机电解液Mg(SnPh3)2的研究

合成了可用于可充镁电池的一种新型电解液Mg（SnPh3）2,其分解电压为1.2V（相对Mg参比）。循环伏安、交流阻抗和电化学性能测试结果表明用它作为可充镁电池的电解液,电池有较好的循环性能。     

Nanostructured Ni3Sn2 thin film as anodes for thin film rechargeable lithium batteries

Thin film Ni₃Sn₂ anodes were deposited on a Cu substrate by e-beam evaporator at room temperature. The deposited films were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). They were tested as anodes for thin film rechargeable lithium batteries. These film electrodes exhibited an excellent cycle performance over 500 cycles. Ni₃Sn₂ films remained without undergoing any crystallographic phase change during cycling.     

硫化类聚乙炔电池的研究

用硫化类聚乙炔材料作正极活性物质,锂为负极,2 mol/L LiClO_4的二氧戊环溶液作电解液,制成了二次电池.对电池的性能进行了研究.实验结果表明,此电池具有很高的比能量,按正极活性物质计算高达1500～2000 W·h/Kg.     

Sulfur composite cathode materials: comparative characterization of polyacrylonitrile precursor

The electrochemical behavior of the sulfur composite cathode material for rechargeable lithium batteries and the characteristic of the polyacrylonitrile precursor were investigated. The samples of different polyacrylonitrile precursors were characterized by thermogravimetric analysis, nuclear magnetic response, Fourier transform infrared spectrometer, and differential scanning calorimetry. The electrochemical performance of the sulfur composite cathode material made from the polyacrylonitrile precursor was also tested. The analysis showed that the molecular weight distribution and the impurity of the polyacrylonitrile precursor affected the electrochemical performance of the sulfur composite cathode material made from the precursor. The polyacrylonitrile precursor with the narrower distribution of the molecular weight and the higher structural purity of the polyacrylonitrile precursor led the better electrochemical performance of the sulfur composite cathode material made from the precursor.     

热处理温度对锂氧气电池用Co-N/C催化剂催化性能的影响

开发低成本、高效的空气电极催化剂是发展锂空气电池的关键课题之一. 采用邻菲咯啉(phen)为配体制备Co(phen)₂配合物,负载于BP2000 碳载体上,并分别在600、700、800 和900 ℃的温度下进行热处理,制备得到碳支撑的Co-N催化剂(Co-N/C). 对催化剂的氧还原反应/析氧反应(ORR/OER)活性进行了表征,并且与典型的CoTMPP/C催化剂进行了比较. 同时研究了煅烧温度对Co-N/C催化剂的组成和结构的影响. 电化学测试结果表明,热处理温度为700-800 ℃时催化剂具有较好的电化学性能. Co-N/C催化剂具有电化学性能优良与低成本的特点,是一种良好的锂氧气电池催化剂.