掺钛尖晶石锂锰氧化物的合成、结构及电化学性能研究

以掺钛电解二氧化锰为锰源合成了一系列掺钛尖晶石锂锰氧化物样品.实验结果表明,无论是在新制样品40次循环的充放电实验中,还是在经过40次循环充放电并在放电状态下贮藏3个月的再次充放电实验中,掺钛样品均具有极好的电化学性能.600℃掺钛样品在第一循环中的放电容量达到206mA·h/g.在放电态贮藏3个月后,再次充放电实验中,第一循环的放电容量达到144mA·h/g.XRD分析表明,掺钛样品仍然具有立方结构.还用红外和拉曼光谱技术研究了钛对尖晶石锂锰氧化物的电化学性能的改善作用.     

层状结构LiMn_(1-x)Cr_xO_2材料合成电化学性能研究

应用流变相法合成掺Cr层状结构锂锰氧化物.XRD分析显示,掺Cr后的锂锰氧化物为单斜晶系(Monoclinic)的层状化合物,而未掺Cr的产物结构则属斜方晶系(Orthorhombic).TEM观测表明,以上两种产物的颗粒都非常细小,直径在60300nm之间,呈球形,且分布均匀.作为锂离子电池正极材料,掺Cr产物的初始容量(>180mAh·g-1)远大于未掺杂的,室温下以50mA·g-1的速率充放40周后仍可保持94%的容量.电化学测试表明,掺Cr的锂锰氧化物能抑制层状结构进一步向尖晶石相转变,从而使其循环能够稳定在2.04.4V范围内.     

尖晶石型LiMn_2O_4的低温制备

锂锰氧化物作为锂离子电池正极材料一直引起人们很大的兴趣.其原材料成本低、资源丰富,用它作成的电极具有电压高、循环寿命长、耐过充放电性能好以及无毒性等优点.而尖晶石型LiMn2O4则是作为下一代锂离子电池最有前途的电极材料之一.经典的制备方法采用固相反应法,煅烧温度高,反应时间长,产物易团聚形成大颗粒.近年来发展了一些低温技术合成锂锰氧化物材料,如溶胶凝胶法[1],沉淀法[2],Penichi法[3]等.这些方法的煅烧温度较低,易得到颗粒小,比表面积大的锂锰氧化物.我们用溶胶凝胶法制备了纳米颗粒的尖晶石型结构的LiMn2O4,用TEM、XRD…     

Li1+xMn2O4的溶胶-凝胶法合成及其电化学性能

锂离子电池;锂锰氧化物;尖晶石结构;Li1+xMn2O4的溶胶-凝胶法合成及其电化学性能     

尖晶石锂锰氧结构中的氧缺陷及其修复方法

研究了氧缺陷型尖晶石锂锰氧化物的结构与电化学性能, 根据缺陷化学理论提出了弥补氧缺陷的办法. X射线衍射(XRD)结果表明, 在真空条件下于750 ℃焙烧不同时间后锂锰氧化物主要物相仍可保持尖晶石结构, 并伴随有少量Mn₃O₄和Li₂MnO₃杂相. 充放电测试及交流阻抗结果表明, 锂锰氧化物材料的放电容量随氧缺陷的增加而降低, 随着氧缺陷的增大, 表面膜阻抗及电荷传递阻抗增大、锂离子在锂锰氧固体中的嵌入与累积量减小使电化学性能恶化. 加入LiOH•H₂O和通入氧气焙烧可在一定程度上修复氧缺陷.     

黄铜矿及其复合材料在电化学储能领域的研究进展

黄铜矿(CuFeS₂)是一种具有特殊金色光泽的天然矿物,具有四方结构,其中Fe、Cu离子与晶格中的硫形成四面体配位,相较于其他硫化物和其相对应的氧化物,CuFeS₂具有较高的电导率和优异的电化学性能,且拥有成本低廉、存在天然矿物且自然储量丰富、无毒等优势,使其具有应用于电化学储能体系电极材料的潜能。本文详细介绍了CuFeS₂的物理化学性质、几种简单的不同形貌的合成方法以及其作为电化学储能电极材料方面的研究,并对CuFeS₂材料未来的研究方向进行了展望。     

掺锶尖晶石相-LiSr_xMn_(2-x)O_4的合成和电化学性能研究

采用固相合成方法制备掺锶尖晶石型锂锰氧化物 ,通过X射线衍射法对材料的结构进行了表征 .结果表明 ,当掺入的锶含量较低时 ,得到的产物具有尖晶石结构特征 ,并表现出极佳的电化学性能 ,材料在充放电循环 90周次后仍能保持 95%的容量     

掺杂Y~(3+)的锂锰尖晶石的合成及其电化学性能研究

采用流变相反应法合成了掺杂稀土钇离子的锂锰尖晶石LiYxMn2 -xO4 ,并对其结构和电化学性能进行了初步研究.结果表明,当掺入的Y3+的含量较低(x≤ 0 0 2 )时,得到的产物能保持完整的尖晶石结构,并表现出极佳的电化学性能.Y3+的掺入使材料的循环稳定性能大幅度提高,而这种提高是源于Y3+对尖晶石结构的稳定作用.电极材料LiY0.0 2 Mn1.98O4 显示了最优的电化学性能,在 0 2C放电速率下,其初始放电容量为 118mA·h·g-1,10 0次循环后仍能保持初始容量的 98%     

锰源对尖晶石LiMn2O4高温性能的影响

为考察不同锰源对所制备尖晶石LiMn₂O₄(LMO)电化学性能的影响(特别是高温性能),采用沉淀法制备前驱体,通过不同煅烧温度制备得到最常用的锰氧化物(MnO₂、Mn₂O₃和Mn₃O₄)为锰源,经相同条件制备得到LMO正极材料,通过考察所得LMO形貌及电化学性能来研究锰源与LMO电化学性能的关系。研究结果表明,相同的前驱体在不同煅烧温度下可以得到不同的锰氧化物,且各自具有不同的形貌结构。由这些锰氧化物都可以得到高纯度的LMO,但产物形貌结构以及材料中的八面体晶体含量和尺寸不同。由Mn₂O₃制备得到的LMO材料中的八面体晶体含量最多,且尺寸最均匀,在3种LMO中容量性能、倍率性能和循环性能最好：0.2C(1C=148 mA·g^-1)下首次放电比容量为131.8 mAh·g^-1;3C下还有100.4 mAh·g^-1的放电比容量。其...     

碳纳米管复合材料的制备、表征和电化学性能

作为锂离子电池负极材料,碳纳米管和金属锡或其氧化物都曾引起过人们浓厚的兴趣,但由于其自身的缺陷,这些材料均未能得到进一步的发展.本文以不同方法合成了碳纳米管和金属锡或其氧化物的复合材料,对其结构、形貌进行表征,并考察它的电化学性能.     

Hydrous manganese oxide/carbon nanotube composite electrodes for electrochemical capacitors

A novel type of composite electrode based on hydrous manganese oxide and a single-walled carbon nanotube has been prepared and used in electrochemical capacitors. Cyclic voltammetry, galvanostatic charging/discharging tests and electrochemical impedance measurements were applied to investigate the performance of the composite electrodes with different ratios of hydrous manganese oxide and single-walled carbon nanotube. For comparison, the performance of pure hydrous manganese oxide and pure carbon nanotubes was also studied. In this way, the composite electrode with a 6:4 ratio of hydrous manganese oxide to carbon nanotube was found to be the most promising active material for an electrochemical capacitor, which shows both good capacitance and power characteristics.     

纳米钒氧化物的制备和机理研究进展

钒氧化物由于其特殊的层状结构和接近室温下的热致相变性质,其纳米结构材料在电化学、催化、光信息存储、光致变色等领域的应用受到越来越多的关注。本文总结了不同维度(包括零维、一维和二维)钒氧化物纳米材料的主要制备方法(水热-溶剂热法、溶胶-凝胶法、反应溅射法等)及其形成机理,并对今后的研究工作进行了展望。     

高分散费—托合成铁／活性炭催化剂的研究：Ⅴ.锰的助剂作用

使用原位穆斯堡尔谱和微型反应器考察了物相、锰含量和制备方法对Fe-Mn/AC催化剂F-T反应性的影响,并讨论了Fe-Mn/AC催化剂的表面结构及其与F-T反应性的关系。对于Fe-Mn/AC催化剂,将铁还原到金属态时具有很高的活性和对气态烯烃和高碳烃的选择性,锰含量对催化剂的活性和选择性影响不大;影响催化剂选择性的主要是受制备制约的铁-锰在活性炭载体表面的结构形态,对此我们提出了模型,只有当铁-锰处于高分散状态,作为助剂锰才能改善催化剂对气态烯烃和高碳烃的选择性,否则锰反而起不利的作用。     

锂离子电池锂锰氧化物高压嵌锂材料的结构和电化学性能研究

利 用 Ｘ Ｒ Ｄ、 Ｉ Ｃ Ｐ、 Ｔ Ｇ Ａ 、 Ｄ Ｔ Ａ 及 恒 流 充 放 电 等 方 法 研 究 分 析 了 一 种 特 殊 天 然 结 构 Ｍｎ Ｏ２（ Ｎ Ｍ Ｄ） 材料的结 构、组成 以及电 化学嵌锂 特性． Ｘ Ｒ Ｄ 分析 表明,该样 品材料 是由钠水 锰矿以及水羟 锰矿复 合结构组 成的 Ｍｎ Ｏ２ 纳米 纤 维． 充放 电 循环 结果 显 示,其 前 期循 环容 量 可高 达 １５０ｍ Ａｈ／ ｇ 左 右,但性 能尚不够 稳定． 本文采 用一种 水热法高 压嵌锂处 理,可将 Ｎ Ｍ Ｄ 样品 转变为 具有３ ×３ 大隧道结 构的钡 镁锰矿（ Ｔｏｄｏｒｏｋｉｔｅ） 型锂 锰氧 化 物,既 增 强了 Ｌｉ ＋ 嵌 入 隧道 或 层间 结 构 的循环稳定 性． 并 显著提 高锂锰氧 化物电 极材料性 能的 稳定 性,以 充放 电电 流密 度 为０ ．８ ｍ Ａ／ｃ ｍ ２ ,经过１８０ 次 循环后 其比容量 仍具有 １１０ ｍ Ａｈ／ ｇ ． 该类 大隧道结 构锂锰 氧化物可 作为一 种３ Ｖ 的锂离子电极 材料．     

Effects of Metal Ion Sources on Synthesis and Electrochemical Performance of Spinel LiMn2O4 Using Tartaric Acid Gel Process

The effect of lithium and manganese ions on the synthesis, phase purity, and electrochemical properties of tartaric acid gel processed lithium manganese oxide spinel were investigated. The poor bonding between both lithium and manganese ions with tartaric acid was shown by the FT-IR analysis when lithium nitrate and/or manganese nitrate were used as sources. Li₂MnO₃ and Mn₂O₃ impurities formed in addition to lithium manganese oxides when nitrate salts were used as the sources. When acetate salts were used as sources for the lithium and manganese ions, single-phase LiMn₂O₄ was obtained. These results indicate that homogeneous bonding between acetate salt and tartaric acid was formed. The capacity of single-phase LiMn₂O₄ calcined at 500°C was 117 mAh/g which was much higher than those containing Mn₂O₃ and Li₂MnO₃ impurity compounds. Thus, sources of lithium and manganese ions play an important role in the synthesis and electrochemical behaviors of lithium manganese oxide spinel.     

脉冲阳极电沉积制备锰氧化物涂层电极

采用脉冲阳极电沉积工艺制备掺杂的锰氧化物涂层电极, 并利用FESEM、SEM、XRD及电化学等方法研究了涂层电极的形貌、相结构及性能. 结果表明, 该方法通过脉冲参数的调整, 可获得优异的电催化性能与稳定性能的涂层电极. 当脉冲频率(f)为90 Hz, 脉冲通断比为1:2时, 具有较大的镀速, 获得较厚的涂层; 氧化物为独特的纳米线与近球状纳米颗粒共聚的网络结构, 不仅增加了电极的电催化活性, 而且有效提高了电极的使用寿命,加速寿命达到1635 h, 比直流阳极电沉积提高55.3%.     

氯酸钾二氧化锰实验室制氧法探原

Oxygen preparation by potassium chlorate and manganese dioxide is one of the most classical laboratory method. Few study has been made so far on its origination and establishment. Through checking the original roles of potassium chlorate and manganese dioxide, it is found that manganese dioxide was ever first selected as raw material for making oxygen, then led the discovery of chlorine by Scheele and potassium chlorate by Berthollet. Potassium chlorate itself was also ever used for oxygen preparation at a high temperature. In 1832, manganese dioxide was firstly mixed with potassium chlorate for oxygen by Döbereiner and reduces the temperature dramatically. With more following studies, the classic method of oxygen preparation via the two materials was finally established.     

用于超级电容器的锰钴氧化物/碳纤维材料

The development of high-performance supercapacitor electrode materials is imperative to alleviate the ongoing energy crisis. Numerous transition metals (oxides) have been studied as electrode materials for supercapacitors owing to their low cost, environmental-friendliness, and excellent electrochemical performance. Among the developed binary transition metal oxides, manganese cobalt oxides typically show high theoretical capacitance and stable electrochemical performance, and are widely used in the electrode materials of supercapacitors. However, the poor conductivity and active material utilization of manganese cobalt oxide-based electrode materials limit their potential capacitance application. Cotton is mainly composed of organic carbon-containing materials, which can be transformed to carbon fibers after calcination. The resultant carbonaceous material exhibits a large specific surface area and good conductivity. Such advantages could potentially suppress the negative effects caused by the poor conductivity and small specific surface area of manganese cobalt oxides, thereby improving the electrochemical performance. Herein, we firstly deposited manganese cobalt oxides on cotton by a simple hydrothermal method, yielding a composite of manganese cobalt oxides and carbon fibers via subsequent calcination, to improve the electrochemical performance of the electrode material. X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET), thermogravimetric analysis (TGA), and electrochemical characterizations were used to investigate the physical, chemical, and electrochemical properties of the prepared samples. The fabricated manganese cobalt oxides in the composite were uniformly dispersed on the carbon fiber surface, which increased the contact between the interface of the electrode material and electrolyte, and enhanced electrode material utilization. The electrode material was confirmed to have well contacted with the electrolyte during a contact angle test. Hence, a pseudo-capacitance reaction completely occurred on the manganese cobalt oxide material. Moreover, the addition of carbon fibers reduced the resistance of the material, resulting in excellent capacitive performance. The capacitance of the prepared composite was 854 F∙g^-1 at a current density of 2 A∙g^-1. The capacitance was maintained at 72.3% after 2000 cycles at a current density of 2 A∙g^-1. These results indicate that the manganese cobalt oxide and carbon fiber composite is a promising electrode material for high-performance supercapacitors. The findings presented herein provide a strategy for coupling with carbon materials to enhance the performance of supercapacitor electrode materials based on manganese cobalt oxides. Thus, novel insights into the design of high-performance supercapacitors for energy management are provided.     

Hierarchical Surface Atomic Structure of a Manganese‐Based Spinel Cathode for Lithium‐Ion Batteries

The increasing use of lithium‐ion batteries (LIBs) in high‐power applications requires improvement of their high‐temperature electrochemical performance, including their cyclability and rate capability. Spinel lithium manganese oxide (LiMn₂O₄) is a promising cathode material because of its high stability and abundance. However, it exhibits poor cycling performance at high temperatures owing to Mn dissolution. Herein we show that when stoichiometric lithium manganese oxide is coated with highly doped spinels, the resulting epitaxial coating has a hierarchical atomic structure consisting of cubic‐spinel, tetragonal‐spinel, and layered structures, and no interfacial phase is formed. In a practical application of the coating to doped spinel, the material retained 90 % of its capacity after 800 cycles at 60 °C. Thus, the formation of an epitaxial coating with a hierarchical atomic structure could enhance the electrochemical performance of LIB cathode materials while preventing large losses in capacity.     

On the use of the reverse micelles synthesis of nanomaterials for lithium-ion batteries

The reverse micelles procedure is a convenient route for the preparation of nanomaterials. Chemical reactions in aqueous media are carried out within a restricted volume, limited by the array of surfactant molecules. The versatility of this technique allows its use in the preparation of different electrode materials for lithium-ion batteries. The thermolysis of the reagents in aqueous solution in the micellar volume by contact with hot kerosene allows the preparation of LiCoO₂, LiMn₂O₄, and LiNi_0.5Mn_1.5O₄ fine powders with good electrochemical behavior. The conversion electrode material Co₃O₄ was prepared with controlled particle size and microstructure by a precipitation reaction in the micellar volume. The electrochemical response found in lithium cells was excellent after optimizing the annealing procedure. Cobalt and iron oxalate nanoribbons and submicrometric rhombic particles of manganese carbonate have been prepared by the reverse micelles procedure and partially behave as conversion oxide electrodes. The electrochemical reaction with lithium of these new oxysalt materials takes place by a different conversion reaction than the corresponding oxide, and a surface capacitive contribution has also been detected.