聚噻吩/纳米MnO2复合材料的制备表征及电化学性能

纳米二氧化锰（MnO₂）作为超级电容材料已被广泛研究。为了改善其充放电性能,采用原位化学氧化聚合法制备聚噻吩/纳米MnO₂ （PTh/MnO₂）复合材料,对纳米MnO₂进行性能改性。通过改变聚噻吩在PTh/MnO₂复合材料中的掺杂量,制备出一系列的复合材料。采用傅里叶转换红外光谱（FIIR）、X射线衍射仪（XRD）、场发射扫描电子显微镜（FE-SEM）和透射电子显微镜（TEM）对PTh/MnO₂复合材料的化学性能、晶体结构以及表面形貌等进行了详细考察。接着采用CT001A型电池测试系统对以PTh/MnO₂复合材料做负极所制得的密封扣式电池进行了充放电性能测试。结果表明,MnO₂和聚噻吩在不同的PTh/MnO₂复合材料中形貌各异。当聚噻吩含量为8wt%~10wt%时,MnO₂在PTh/MnO₂复合材料中分布最为均匀;当聚噻吩含量较高时,MnO₂的形貌受到严重影响,其原来的管状结构接近消失。聚噻吩含量的不同,同样也影响了电池的充放电性能。当聚噻吩的含量为20wt%时,在循环20次后,电池的平衡容量为最高,可达700 mAh/g。这明显高于以纳米MnO₂为负极时的电池容量。由此可见,聚噻吩对纳米MnO₂的充放电性能具有明显的增强作用。该研究为PTh/MnO₂复合材料作为电池负极材料的使用提供了实验基础。     

Comparison of the electrochemical behavior of CeO2–SnO2 and CeO2–TiO2 electrodes produced by the Pechini method

CeO₂–SnO₂ and CeO₂–TiO₂ thin films were prepared by the Pechini method and their characteristics were compared, using a fractional factorial design to quantify the effect of five preparation variables. It was observed that CeO₂–SnO₂ electrodes show a greater electrochemical response than the CeO₂–TiO₂ films. The best intercalation charge densities were 18.11 and 9.91 mC/cm² for CeO₂–SnO₂ and CeO₂–TiO₂, respectively. Both films were optically inactive with transparencies, in most cases, higher than 90%.     

MnO2纳米棒-还原石墨烯复合修饰玻碳电极用于苋菜红的检测

利用电化学还原法制备MnO₂纳米棒-还原石墨烯复合修饰电极（MnO₂ NRs-ErGO/GCE）用于苋菜红的检测。采用SEM和XRD分别对修饰电极材料进行微观形貌和成分结构表征。通过循环伏安法考察了苋菜红在裸电极、ErGO/GCE和MnO₂ NRs-ErGO/GCE上的电化学行为,并对测定条件如pH值、富集电位、富集时间进行了优化。结果表明,MnO₂ NRs-ErGO增大了GCE电化学活性面积,提高了苋菜红的电化学氧化响应。在最优的检测条件下,MnO₂ NRs-ErGO/GCE线性扫描伏安法检测苋菜红线性范围为2.0×10^-8~1.0×10^-5 mol/L和1.0×10^-5~4.0×10^-4 mol/L,检测限为1.0×10^-8 mol/L。MnO₂ NRs-ErGO/GCE用于真实饮料样品检测,获得满意结果。     

MnO_(2)纳米棒的吸波性能及其超构表面设计EI北大核心CSCD

采用水热法和冷冻干燥技术制备MnO_(2)纳米棒材料,并利用模压法制备不同填充浓度的MnO_(2)/石蜡环状样品。通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)、矢量网络分析仪(VNA)对样品的物相、微观结构、电磁参数进行了表征与测试,利用CST软件模拟设计了样品材料的超构表面,并对其设计前后的电磁波反射率进行了模拟计算与研究。结果表明:制备的MnO_(2)粉体呈棒状结构,棒体直径约50-100 nm,长度约5-10μm,单根结构圆柱度高,整体的结构均一性和结晶度好;MnO_(2)/石蜡样品的电磁衰减系数(α)随MnO_(2)纳米棒填充浓度的提高而增大,主要得益于随浓度增加而逐渐提升的介电损耗正切值(tanδ);超构表面的设计极大地拓宽了MnO_(2)/石蜡材料的微波吸收频域,2-18 GHz内最优频宽可达14.32 GHz,主要是超构表面引起的多谐振共存使得在规定频率范围内出现了多个吸收峰叠加而实现的。     

多孔球形Li2MnSiO4/C正极材料的制备及电化学性能

采用湿法球磨-喷雾干燥法制备了多孔球形锂离子电池Li2MnSiO4/C复合正极材料。X射线衍射(XRD)表明合成的Li2MnSiO4具有正交结构,属于Pmn21空间群。扫描电镜(SEM)和透射电镜(TEM)显示粉体复合材料为直径10μm左右的球形团簇,由100nm左右的颗粒堆积而成,颗粒表面包覆1层大约3nm的碳层。电化学测试表明,在0.05和0.5C倍率下,Li2MnSiO4/C样品的首次放电容量分别为153和110mAh/g,50次循环后容量分别保持80%和66%。     

Investigation of electrochemical properties of RuO2 thin films modified by e-beam irradiation

The influence of electron beam irradiation on the electrochemical properties of electrodeposited RuO₂ thin films was investigated using a 1 MeV electron beam. Crystallinity change before and after electron beam irradiation was investigated by X-ray diffraction, and the oxidation state of ruthenium was determined by X-ray photoelectron spectroscopy. Scanning electron microscopy was utilized to examine the morphology of the films. The results show that electron beam irradiation altered the oxidation state of ruthenium and increased crystallinity.Cyclic voltammetry was employed to evaluate the electrochemical properties of the synthesized RuO₂ films in terms of their application as electrodes of electrochemical capacitors. RuO₂ irradiated with 40 kGy showed 2.7 times higher capacitance (520 Fg⁻¹) than the as-electrodeposited sample (190 Fg⁻¹).     

Fe3O4/MnO2磁性复合氧化物催化剂的制备及性能

具有磁性的非均相催化剂价格低廉、低污染、高能效、容易从溶液中分离出来。经过水热合成法合成的Fe₃O₄/MnO₂磁性复合氧化物催化剂在活化过一硫酸盐（2KHSO₅·KHSO₄·K₂SO₄）产生硫酸根自由基（SO₄-）降解水中有机污染物表现出了优良的性能。把不同质量的磁性Fe₃O₄微球与线状的MnO₂负载到一起,合成三种Fe₃O₄:MnO₂质量比分别为1:3、2:3、1:1的Fe₃O₄/MnO₂催化剂,经过XRD、SEM和TEM表征,表明这两种金属氧化物负载到一起。对比不同Fe₃O₄:MnO₂质量比的Fe₃O₄/MnO₂磁性复合氧化物催化剂活化2KHSO₅·KHSO₄·K₂SO₄的活性,发现Fe₃O₄/MnO₂（2:3）催化剂催化活性最高。通过考察不同因素对Fe₃O₄/MnO₂（2:3）催化活性的影响得出,水中罗丹明B（Rh B）降解的最佳条件为10 mg/L Rh B、0.4 g/L Fe₃O₄/MnO₂催化剂、0.3 g/L 2KHSO₅·KHSO₄·K₂SO₄、pH=8。Fe₃O₄/MnO₂（2:3）磁性复合氧化物催化剂经过3次循环利用后,催化活性没有明显下降。SO₄-在降解水中Rh B起主要作用。      

Facile synthesis of MnO2/CNT nanocomposite and its electrochemical performance for supercapacitors

A nanocomposite of manganese dioxide coated on the carbon nanotubes (MnO₂/CNTs) was synthesized by a facile direct redox reaction between potassium permanganate and carbon nanotubes without any other oxidant or reductant addition. The morphology, microstructure and crystalline form of this MnO₂/CNT nanocomposite were characterized by scanning electron microscopy (SEM), transition electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The electrochemical properties are characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge/discharge (GCD). The results show that the facile prepared MnO₂/CNTs nanocomposite shows specific capacitance of 162.2 F g⁻¹ at the current density of 0.2 A g⁻¹ and excellent charge/discharge property with 90% of its specific capacitance kept after 2000 cycles at the current density of 5 A g⁻¹.     

Sensitivity enhancement for H2 gas detection using a SnO2–Ag2O–PdOx nanocrystalline system

Thick film H₂ sensors were fabricated using SnO₂ loaded with Ag₂O and PdO_x. The composition that gave highest sensitivity for H₂ was in the wt.% ratio of SnO₂:Ag₂O:PdO_x as 93:5:2. The nano-crystalline powders of SnO₂–Ag₂O–PdO_x composites synthesized by sol–gel method were screen printed on alumina substrates. Fabricated sensors were tested against gases like H₂, CH₄, C₃H₈, C₂H₅OH and SO₂. The composite material was found sensitive against H₂ at the working temperature 125 °C, with minor interference of other gases. H₂ gas as low as 100 ppm can be detected by the present fabricated sensors. It was found that the sensors based on SnO₂–Ag₂O–PdO_x nanocrystalline system exhibited high performance, high selectivity and very short response time to H₂ at ppm level. These characteristics make the sensor to be a promising candidate for detecting low concentrations of H₂.     

Effect of Fe on the synthesis and electrochemical performance of nanostructured MnO2

Different MnO₂ nanostructures were synthesized in stoichiometric KMnO_4/MnSO₄ aqueous solutions in the absence/presence of Fe³⁺ at temperature ranging from 30 °C to 180 °C. The phase structures, morphologies and electrochemical properties of the as-prepared MnO₂ products were investigated using X-ray powder diffraction, scanning electron microscope, N₂ physical adsorption and cyclic voltammetry techniques. The results showed that the presence of Fe³⁺ addition had a significant effect on the phase structural evolution, morphological features and electrochemical properties of the MnO₂ products. Fe³⁺ was found to greatly prevent the epitaxial growth and crystallization of MnO₂ nucleus, which in turn influenced textual characteristics. The electrochemical performance of the nanostructured MnO₂ products had a complex relationship with the phase structures, specific surface area as well as pore characteristics. MnO₂ prepared in the presence of Fe³⁺ (KMF-MnO₂) showed relatively higher specific capacitance compared to that of MnO₂ prepared in the absence of Fe³⁺ (KM-MnO₂). Maximum capacitance of 214 F g⁻¹ was obtained for KMF-MnO₂ prepared at 30 °C at a scan rate of 2 mV s⁻¹ in 0.1 M Na₂SO₄ electrolyte.     

复合磁性催化剂β-MnO2/MnxZn1-xFe2O4的制备与表征

采用化学共沉淀法制备了以Mn_xZn_1-x Fe₂O₄为磁性基体的β-MnO₂/Mn_xZn_1-xFe₂O₄复合磁性催化剂,利用XRD、SEM、FTIR和超导量子干涉仪对复合磁性催化剂的结构和性能进行了表征,以罗丹明B （RhB）为模拟污染物,研究了β-MnO₂/Mn_xZn_1-xFe₂O₄的催化活性,并考察了其稳定性。结果表明,球状的β-MnO₂与块状的磁性基体Mn_xZn_1-xFe₂O₄成功复合,且制备的β-MnO₂/Mn_xZn_1-xFe₂O₄复合磁性催化剂具有良好的催化性能和磁学性能。当Mn_xZn_1-xFe₂O₄与β-MnO₂的质量比为20：100时,在2 mL含量为30%的H₂O₂作用下,1 h内β-MnO₂/Mn_xZn_1-xFe₂O₄复合磁性催化剂对100 mL浓度为10 mg/L的RhB降解率（93.9%）远高于纯β-MnO₂（33.7%）;在磁场作用下,β-MnO₂/Mn_xZn_1-xFe₂O₄复合磁性催化剂的回收率为89%,经过5次循环利用之后其对RhB的降解率仍达76%。     

NiCo2O4/氧化石墨烯复合材料制备与电化学性能研究

为了研究NiCo₂O₄/氧化石墨烯(NiCo₂O₄/GO)复合材料的电化学性能,本文通过先水热合成前驱体再煅烧的方法制备了一系列NiCo₂O₄/GO复合材料.利用X射线衍射(XRD)、扫描电子显微镜(SEM)和电化学方法对其进行物理表征,其中以GO质量浓度为1 mg/mL悬浊液制备出的NiCo₂O₄ /GO-3复合材料呈类海胆状结构.在1 M KOH水溶液中使用循环伏安法、恒电流充/放电法和交流阻抗法研究了NiCo₂O₄/GO复合材料电化学性能.研究表明,与纯NiCo₂O₄相比,制备的NiCo₂O₄ /GO复合材料的比容量和赝电容性能均有明显提高,这主要是由于NiCo₂O₄ /GO复合材料中NiCo₂O₄与GO纳米片的相互作用形成的高孔隙率复合结构;NiCo₂O₄ /GO-3复合材料在电流密度为0.5~3.0 A/g时,比电容超过650 F/g,具有良好的倍率性能和高比容量.采用本文方法合成的NiCo₂O₄/GO复合材料,既提高了其倍率性能又保证了高比容量,是一种良好的超级电容器电极材料.     

Effects of growth conditions on the domain structure and dielectric properties of (1 − x)Pb(Sc1/2Nb1/2)O3–xPbTiO3 single crystals

The studies of the (1 − x)Pb(Sc_1/2Nb_1/2)O₃–xPbTiO₃ (PSN–PT) single crystals reveal that the chemical and physical properties of the materials are affected by the growth conditions. By the measurements of the dielectric constant as a function of temperature upon cooling, it is found that crystals grown from the same charged stoichiometric composition (x = 0.425), but under different flux environments (i.e. the composition of flux and the flux to PSN–PT ratios are varied), show anomalies (i.e. phase transitions) at different temperatures. This phenomenon is attributed to the complex local chemical structure of the PSN–PT solid solution single crystals with B-site random occupancy of three different cations (Sc³⁺, Nb⁵⁺ and Ti⁴⁺). The dielectric and domain structure of the PSN–PT crystals with composition near the morphotropic phase boundary (MPB) are investigated, showing much more complex situations compared with Pb(Sc_1/2Nb_1/2)O₃.     

苯胺-SrTi(C2O4)2颗粒制备及其电流变性能

用沉淀法制备了苯胺-草酸氧钛锶（SrTi（C₂O₄）₂）颗粒。FTIR分析表明,苯胺已引入到SrTi（C₂O₄）₂颗粒的表面;XRD分析表明,苯胺-SrTi（C₂O₄）₂颗粒为含少量结晶的无定形态。采用SEM观察颗粒的形貌,结果表明,随反应体系中苯胺与钛原子物质的量比n_aniline/n_Ti的增大,苯胺-SrTi（C₂O₄）₂颗粒由近似球状（n_aniline/n_Ti =0）变为多面体状（n_aniline/n_Ti =2）,而后变为棒状与团簇状颗粒的混合体系（n_aniline/n_Ti =3）。以苯胺-SrTi（C₂O₄）₂颗粒为分散相制备颗粒质量分数为66.7%电流变液,电流变性能测试结果表明,在n_aniline/n_Ti =2时,电流变液具有较高的剪切应力和剪切屈服强度、较大的漏电流密度。苯胺在颗粒制备过程中起控制颗粒形貌的作用,在电流变液体系中起极性分子的作用,其对苯胺-SrTi（C₂O₄）₂电流变液性能的影响是两种效应综合作用的结果。     

Synthesis and shape evolution of novel cuniform-like MnO2 in aqueous solution

In this paper, the cuniform-like MnO₂ particles were first successfully synthesized with dodecylbenzenesulfonic acid (DBSA) as surfactant in aqueous solution. The samples were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and infrared spectroscopy (IR). The possible mechanisms of the shape evolution for the formation of MnO₂ samples were discussed.     

Fluorescence line narrowing study of Cr ions in cordierite glass nucleating MgAl2O4 nanocrystals

The luminescence of Cr³⁺ ions in cordierite glass nucleating MgAl₂O₄ nanocrystallites has been investigated. The time resolved fluorescence line narrowing measurements and the temperature dependence of the homogeneous line width show that most Cr³⁺ ions are inside the nanocrystallites. Cr³⁺ ions occupy non-equivalent crystal sites, due to the Mg²⁺–Al³⁺ inversion effect. The values of the homogeneous line width compare well with those of previous studies in crystals. No surface effect has been observed due to the large size of the crystals.     

Er3+/Yb3+掺杂NaGd(WO4)2粉体的制备与发光性能

采用水热法成功制备了Er~(3+)/Yb~(3+)双掺杂的NaGd(WO_4)_2纳米粉体,研究了不同络合剂、水热温度对样品形貌和结构的影响。测量了不同Er~(3+)掺杂浓度样品的可见上转换和近红外发射光谱。结果表明:在980nm LD激发下,可观测到样品强烈的绿色上转换发光,对应Er~(3+)的~2H_(11/2)→~4I_(15/2)(530nm)和~4S_(3/2)→~4I_(15/2)(552nm)跃迁,以及较弱的红色上转换和近红外发光,分别对应Er~(3+)的~4F_(9/2)→4I15/2(656nm)和~4I_(13/2)→~4I_(15/2)(1 532nm)跃迁。且随着Er~(3+)掺杂浓度的增加,样品的上转换红绿光和1.54μm附近的近红外光均呈现出先增大后减小的趋势。样品的激发和发射光谱显示,在378nm处的激发峰最强,对应Er~(3+)的~4I_(15/2)→~4 G_(11/2)能级跃迁,最强发射峰位于552nm。根据泵浦功率与发光强度的关系可以得出,红光和绿光的发射主要为双光子吸收过程,但红光还包含了一定的单光子吸收成分。     

Determining crystallization kinetic parameters of Li2O–Al2O3–SiO2 glass from derivative differential thermal analysis curves

The kinetic parameters such as crystallization activation energy, E, and the frequency factor, ν, of Li₂O–Al₂O₃–SiO₂ glass were determined by a new non-isothermal method. The method is described by the equation

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, where β is the heating rate and T_f is the inflection-point temperature of differential thermal analysis (DTA). The value of T_f is determined as the maximum peak temperature on derivative differential thermal analysis (DDTA) curves. Values of E and ν of Li₂O–Al₂O₃–SiO₂ glass were also determined by two existing non-isothermal methods, namely the Kissinger plot and the Ozawa plot, and compared with those determined by isothermal method. Values of E and ν determined by the proposed equation were 332 kJ/mol and 1.4×10¹³ s⁻¹, respectively. They are excellent agreement with the isothermal analysis results, 336 kJ/mol and 1.8×10¹³ s⁻¹, respectively. In contrast, both the Kissinger equation and the Ozawa equation give much higher values of E and ν.     

Rapid synthesis of homogeneous MnO2/multi-wall carbon nanotubes nanostructure and its electrochemical capacitive behavior

A homogeneous composite of MnO₂/multi-wall carbon nanotubes (MnO₂/MWCNTs) was rapidly and efficiently synthesized by a redox reaction of MnO₄⁻ and Mn²⁺ on the MWCNTs under ultrasonic irradiation. The structure and morphology of the obtained MnO₂ and MnO₂/MWCNTs composite were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and transmission electron microscopy. Electrochemical investigation indicated that the maximum specific capacitance of the MnO₂/MWCNTs composite, measured by galvanostatic charge-discharge test, was 315 F g^− 1, compared to the pristine MnO₂ (192 F g^− 1) and MWCNTs electrode (25 F g^− 1), showing the synergistic effect of MWCNTs and MnO₂. The homogeneous hybrid nanostructure and the good conductivity of MWCNTs were considered to be responsible for its preferable electrochemical performances.