腐殖酸基石墨化材料的制备及其电化学性能

以腐殖酸为前驱体,通过高温热处理制备锂离子电池负极材料。采用扫描电子显微镜(SEM)、X射线衍射(XRD)和电化学测试系统对该材料的形貌、微晶结构和电化学性能进行表征。结果表明,腐殖酸基石墨化材料呈现出较为规整的石墨片层结构,且随着石墨化温度的升高,所得材料的石墨化度也越来越高。腐殖酸基石墨化材料均表现出良好的电化学性能,石墨化温度为2 800℃所制备的石墨化材料的首次放电比容量为356.7 mAh/g,充电比容量为277.6 mAh/g,首次充放电的库仑效率为77.81%,在1C和2C倍率下50次充放电循环后的容量保持率分别高达99.4%、95.9%,是一种理想的锂离子电池负极材料。     

Preparation,structure, and electrochemical performance of anodes from artificial graphite scrap for lithium ion batteries

Artificial graphite scrap prepared from petroleum coke with low degree of graphitization was further graphitized under various conditions. Different categories of coke were also treated with the optimum technology. The prepared samples were characterized with X-ray diffraction, ash content determination, morphology observation, and galvanostatic charge and discharge. It was shown in the experiments that the heat treatment temperature should be increased to 2800 °C to remove impurities. Slow heating rate and evacuation technology were beneficial to the growth of graphite crystallite and the improvement of discharge capacity. And the latter condition possessed the larger influences, especially on the growth of crystallite dimension in the b axis direction, degree of graphitization, and discharge capacity. The sample D-3000 prepared from pure needle coke possessed the maximum discharge capacity of 342.1 mAhg⁻¹ among all prepared samples. The linear regression equations between the volume of graphite crystallite and discharge capacity were established.     

纳米碳管用于锂离子电池负极材料的研究

采用氧化法提纯了煤焦化工业副产品中的纳米碳管,采用X射线衍射法对纳米碳管的结构进行了研究,透射电镜研究了纳米碳管的形貌。提纯的纳米碳管d002为0.3496nm,具有类似石墨的结构和较高的石墨化度。研究了纳米碳管的电化学性能,其首次放电比容量达584.3mAh/g;添加石墨粉组成了20％的纳米碳管和80％的石墨粉的体系作为锂离子电池负极材料,其首次放电比容量为490.1mAh/g,并有较好的循环性能。     

Boron-doped carbon microspheres as the catalyst for rechargeable Al-air batteries

Three-dimensional mesoporous boron-doped carbon microspheres (B-CMs) were synthesized through a facile impregnation-calcination method. The B atoms introduced plentiful defects into the surfaces of CMs and were mainly presented in the form of boron carbide, which increases the specific surface area of the composite material and endows it with enhanced catalytic activity. A rechargeable aluminum (Al-)-air battery with B-CMs catalysts exhibited low overpotentials and its effective discharge capacity reached 300 mAh g^?1 at the current density of 50?mA g^?1. The capacity of Al-air battery was maintained at 584 mAh g^?1 after 30 cycles.     

Effect of heat treatment temperature on microstructure and electrochemical properties of hollow carbon spheres prepared in high-pressure argon

Heat treatment was carried out between 800 and 1200°C to investigate its effects on the microstructure and electrochemical properties of the hollow carbon spheres (HCSs) prepared in high-pressure argon. Samples were characterized by X-ray diffraction, Raman spectroscopy, field-emission scanning electron microscopy, high-resolution transmission electron microscopy and N₂ adsorption-desorption isotherms. The graphitization of the HCSs was improved with increase of heat treatment temperature. Mesopores of ca. 4 nm in diameter were created on the HCSs after the heat treatment. The results of electrochemical performance measurements for the HCSs as anode material for lithium ion batteries indicate that the discharge capacity of the HCSs is improved after heat treatment at 800°C compared with the as-prepared HCSs and have a maximum value of 357 mAh/g and still retains 303 mAh/g after 40 cycles. However, the discharge capacity of the HCSs decreases and the cycling performance is improved with the increase of heat treatment temperature.     

Synthesis and electrochemical characterization of LiCo<Subscript>1/3</Subscript>Ni<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> by radiated polymer gel method

Layered LiCo_1/3Ni_1/3Mn_1/3O₂ as a lithium insertion positive-electrode material was prepared by a radiated polymer gel method. The synthesis conditions and microstructure, morphology and electrochemical properties of the products were investigated by XRD, SEM and electrochemical cell cycling. It was found that the positive-electrode material annealed at 950 °C showed the best electrochemical property with the first specific discharge capacity of 178 mAh/g at C/6 and stable cycling ability between 2.8 and 4.5 V versus Li/Li⁺. The optimized LiCo_1/3Ni_1/3Mn_1/3O₂ exhibited rather good rate capability with the specific capacity of 173 mAh/g at 0.2C and 116 mAh/g at 4C under a fast charge and discharge mode in rate performance test.     

修饰石墨用作锂离子电池负极材料的研究

采用将高分子聚合物（例如酚醛树脂）包覆于石墨表面形成高分子碳化的方法,对石墨进行表面修饰处理,大大改善了石墨用作锂离子电池负极的性能。通过电化学测试发展,修饰石墨首次充放电效率达到９４．９％,比容量为３０６．１ｍＡｈ／ｇ,并且经过１００次循环后,比容量误差率公为８．２％。通过ＳＥＭ观察和ＸＲＤ衍射分析发现,石墨颗粒表面修饰对颗粒细化,提高锂离子嵌入活性点。防止溶剂分子共嵌入均有增强作用。     

磷铁和碳酸锂制备LiFePO4的反应机理和性能研究

采用碳热还原法以磷铁和碳酸锂为原料合成了LiFePO4,用XRD、恒流充放电法和EIS对其进行表征,用TG-DTA分析了反应过程。预焙烧过程中磷铁中的磷与碳酸锂反应形成Li4P2O7和LiFeP2O7,再与中间产物Fe2O3、Fe3O4和补充磷源NH4H2PO4进一步反应生成LiFePO4。产物具有良好的电化学性能,在0.1C时放电容量可以达到151.68mAh/g,0.2和0.5C分别循环10和20次后放电容量仍有125.94和103.51mAh/g,衰减率分别为4.23%和7.24%。不同荷电状态的EIS结果表明:放电至2.4V具有最小的溶液阻抗;界面阻抗由于充放电至3.4V时包括一部分不稳定的SEI膜,因此比充放电至2.4V时大;随着充放电过程的继续,反应过程由反应控制逐渐变为扩散控制。     

Al2O3修饰改进Li1+xV3O8的电化学性能

采用高温固相法合成了Al2O3修饰的Li1 xV3O8自正极材料,用X射线衍射、恒电流充放电实验、循环伏安法等对材料的结构和电化学性能进行了表征.结果表明Al2O3修饰使得Li1 xV3O8材料的层间距离增大,材料的导电性能和电化学反应的可逆性提高.当Al2O3含量为6mol%时,Li1 xV3O8表现出良好的循环性能,首次放电容量达到219mAh/g,10次循环后容量保持率为92.3%.     

利用碳纳米管增强Li/CFx一次电池的性能

以碳纳米管(Multi-walled carbon nanotubes)为导电添加剂,对锂/氟化石墨(Li/CFx)一次电池正极活性材料氟化石墨进行改性。采用TGA、Raman、SEM、TEM对氟化石墨和碳纳米管进行表征分析。采用恒流放电和电化学阻抗频谱对电池进行检测。结果表明,添加碳纳米管能够有效改善电池的综合性能。碳纳米管添加量为5%(质量分数),在1C放电倍率时,电池的放电比容量达到900mAh/g,并具有2.2V放电电压平台,对比超级炭黑导电剂598.5mAh/g的放电比容量和2V的放电平台,电池放电比容量和电压平台分别提高50.2%和10%,电池的倍率性明显改善。电化学阻抗频谱也显示,添加碳纳米管能有效减小电池的内阻,改善放电性能。     

新型锂离子电池负极材料COFe3Sb12

用高能球磨方法制备出CoFe3Sb12合金粉末,研究了电化学性能。结果表明,CoFe3Sb12中的活性元素Sb可以与锂离子发生可逆电化学反应,其嵌锂产物为Li3Sb。CoFe3Sb12电极在20mA/g的电流密度下第一次可逆容量为396mAh/g。在材料中加入原子分数为50％的石墨（化学计量式为CoFe3Sb12-C16)后,以100mA/g进行充放电时,第一次可逆容量为380mAh/g。电极的循环寿命性能优良。     

High Areal Capacity and Lithium Utilization in Anodes Made of Covalently Connected Graphite Microtubes

Lithium metal is an attractive anode material for rechargeable batteries because of its high theoretical specific capacity of 3860 mA h g^?1 and the lowest negative electrochemical potential of ?3.040 V versus standard hydrogen electrode. Despite extensive research efforts on tackling the safety concern raised by Li dendrites, inhibited Li dendrite growth is accompanied with decreased areal capacity and Li utilization, which are still lower than expectation for practical use. A scaffold made of covalently connected graphite microtubes is reported, which provides a firm and conductive framework with moderate specific surface area to accommodate Li metal for anodes of Li batteries. The anode presents an areal capacity of 10 mA h cm^?2 (practical gravimetric capacity of 913 mA h g^?1) at a current density of 10 mA cm^?2, with Li utilization of 91%, Coulombic efficiencies of ≈97%, and long lifespan of up to 3000 h. The analysis of structure evolution during charge/discharge shows inhibited lithium dendrite growth and a reversible electrode volume change of ≈9%. It is suggested that an optimized microstructure with moderate electrode/electrolyte interface area is critical to accommodate volume change and inhibit the risks of irreversible Li consumption by side reactions and Li dendrite growth for high‐performance Li‐metal anodes.     

锂离子电池正极梯度材料的制备及电性能研究

采用金属离子混合硫酸盐溶液分次共沉淀法制备前躯体,混锂后通过高温固相反应得到具有镍、钴和锰浓度梯度的层状LiNi0.56Co0.22Mn0.22O2锂离子电池正极材料。通过x射线衍射(XRD)、扫描电子显微镜(SEM)及恒电流充放电测试对合成的材料进行了表征。结果表明,750～900℃焙烧15h下合成的产物均具有典型的α-NaFeO2型层状结构特征,晶型结构完整,粒度均匀。800℃合成的正极材料具有较好的电化学性能。在充放电倍率0.4C、2.75-4.2V电压范围内,材料的首次充放电比容量分别为170.0mAh/g和131.8mAh/g,放电效率为77.5%;第51次循环的充放电比容量分别为131.3mAh/g和130.5mAh/g,放电效率为99.4%,容量保持率达到99.0%。     

Synthesization and characterization of FeS2 by mechanical alloying for Na/FeS2 cell

In this study, the FeS2 fine compound powders were synthesized by mechanical alloying (MA) for 15 hrs and stearic acid was added as PCA (Process Control Agent) to prevent the excessive cold welding and agglomeration. For the purpose of ulteriorly reducing the particle size to improve the contact areas between the active materials and conducting agents, the wet ball milling process was applied by employing normal hexane (C6H14) as the milling solvent. The mean particle size of FeS2 powders about 1.14 microm were obtained after 24 hrs wet ball milling. The powders were characterized by FE-SEM, XRD, TEM and EDS. To compare the influence of particle size on the properties of charge/discharge, the same electrolyte was employed for both tests by dissolving 1M NaCF3SO3 (sodium trifluoromethanesulfonate) in a liquid of TEGDME (tetraethylene glycol dimethylether). The first discharge capacity of Na/FeS2 cell made by dry ball milled powders was 440 mAh/g with a plateau potential at approximately 1.25 V versus Na/Na+ and 260 mAh/g at the 25th cycle at room temperature. Meanwhile, the initial discharge capacity of Na/FeS2 cell made by wet ball milled powders was 614 mAh/g with the same discharge plateau potential and retained 385 mAh/g at the 25th cycle. And the discharge capacity for wet milled system decreased continuously by repeated charge/discharge cycling in the first 20 cycles and has little change after 60 cycles, which means the good cycling properties, remaining half of its initial discharge capacity of 320 mAh/g even after 100 cycles.     

锂离子电池用Si/针状焦复合负极材料的改性及其电化学性能

以石墨化针状焦为原料,采用机械球磨和化学气相沉积法(CVD)制得碳/Si/针状焦复合负极材料。结合XRD、SEM分析手段和电化学特征,研究发现:当石墨化针状焦复合20%的纳米Si后,其首次放电容量高达1110mAh/g,但25次循环后放电容量衰减为200mAh/g;采用CVD方法,在Si/针状焦复合材料的表面沉积厚度为6~8nm的碳后,其首次库伦效率为81%,25次循环后放电容量仍能稳定在860mAh/g,且循环效率接近99%。     

锂离子电池正极材料Li3V2-2x/3Mnx（PO4）3的溶胶凝胶法合成和电化学性能

以CH3COOLi·2H2O、V2O5、Mn(CH3COO)2·4H2O、(NH4)2HPO4和蔗糖为原料,采用溶胶–凝胶法合成了掺锰磷酸钒锂/碳(Li3V2-2x/3Mnx(PO4)3/C)复合正极材料,用XRD、XPS、SEM、电化学性能对样品进行了表征.测试结果表明,少量锰的掺杂并未改变Li3V2(PO4)3/C的单斜结构,Li3V1.94Mn0.09(PO4)3中的Mn和V分别以+2和+3价存在,其颗粒类似球形,直径比较均匀且小于200 nm,并表现出良好的电化学性能.在0.1C倍率和3.0～4.8 V电压内,该样品的首次充、放电容量分别为182.1和168.8 mAh/g,放电效率高达92.69%,而且100次循环后,其放电比容量仍是首次放电容量的77.4%.     

快速凝固高碳铁基合金脉冲激光非平衡热处理

利用脉冲Ｎｄ：ＹＡＧ激光辐照对快速凝固高碳铁基合金进行非平衡相变热处理，发现在高能脉冲激光辐照时，原快速凝固共晶碳化物（Ｆｅ３Ｃ）异常迅速地石墨化，获得了含超细石墨球和既含超细石墨球又含快速凝固共晶Ｆｅ３Ｃ的两种新材料，研究表明，这种快速石墨化及上述两类新型材料的形成主要归因于脉冲激光光速辐照产生强烈周期性起伏温度场的“微退火（ｍｉｃｒｏ－ａｎｎｅａｌｉｎｇ）效应。     

Fabricating Ir/C Nanofiber Networks as Free‐Standing Air Cathodes for Rechargeable Li‐CO2 Batteries

Li‐CO₂ batteries are promising energy storage systems by utilizing CO₂ at the same time, though there are still some critical barriers before its practical applications such as high charging overpotential and poor cycling stability. In this work, iridium/carbon nanofibers (Ir/CNFs) are prepared via electrospinning and subsequent heat treatment, and are used as cathode catalysts for rechargeable Li‐CO₂ batteries. Benefitting from the unique porous network structure and the high activity of ultrasmall Ir nanoparticles, Ir/CNFs exhibit excellent CO₂ reduction and evolution activities. The Li‐CO₂ batteries present extremely large discharge capacity, high coulombic efficiency, and long cycling life. Moreover, free‐standing Ir/CNF films are used directly as air cathodes to assemble Li‐CO₂ batteries, which show high energy density and ultralong operation time, demonstrating great potential for practical applications.     

Boron-doped microporous nano carbon as cathode material for high-performance Li-S batteries

In this study,a boron-doped microporous carbon (BMC)/sulfur nanocomposite is synthesized and applied as a novel cathode material for advanced Li-S batteries.The cell with this cathode exhibits an ultrahigh cycling stability and rate capability.After activation,a capacity of 749.5 mAh/g was obtained on the 54th cycle at a discharge current of 3.2 A/g.After 500 cycles,capacity of 561.8 mAh/g remained (74.96％ retention),with only a very small average capacity decay of 0.056％.The excellent reversibility and stability of the novel sulfur cathode can be attributed to the ability of the boron-doped microporous carbon host to both physically confine polysulfides and chemically bind these species on the host surface.Theoretical calculations confirm that boron-doped carbon is capable of significantly stronger interactions with the polysulfide species than undoped carbon,most likely as a result of the lower electronegativity of boron.We believe that this doping strategy can be extended to other metal-air batteries and fuel cells,and that it has promising potential for many different applications.     

碳源对液相法制备Li3V2（PO4）3/C的影响

以4种不同种类的有机物(柠檬酸、水杨酸、聚丙烯酸、蔗糖)为碳源,通过液相反应合成Li3V2(PO4)3/C复合材料。研究了不同碳源对复合材料的晶型结构、形貌及电化学性能的影响。结果表明,碳源对Li3V2(PO4)3/C材料的晶型结构没有影响,但对电化学性能影响较明显,其中采用柠檬酸为碳源制得的Li3V2(PO4)3/C复合材料电化学性能最好。进一步研究了柠檬酸的加入量对复合材料的电化学性能的影响,发现当柠檬酸加入量为钒与碳的物质的量比为1∶4时,样品的平均粒径较小,电化学性能最好,0.1C首次放电比容量为123.59mAhg-1,0.5C首次放电比容量也高达117.27mAhg-1,循环10次后,仍保持在117.19mAhg-1,容量几乎没有衰减,10C时比容量仍有105.43mAhg-1。