Ti/Ru_(0.4)Sn_(0.6-x)Mn_xO_2氧化物电极的电容特性

采用热分解法制备Ti/Ru_(0.4)Mn_(0.6-x)Sn_xO_2(x=0,0.3,0.6)三元氧化物电极材料。通过扫描电子显微镜(SEM)、X射线衍射(XRD)、循环伏安(CV)、交流阻抗谱(EIS)和恒流充放电分析Ti/Ru_(0.4)Sn_(0.6-x)Mn_xO_2电极材料的组织结构和电容性能。结果表明:三元氧化物电极中Sn O_2的加入能抑制Ru O_2表面析出,且有利于形成Ru-Mn-Sn-O固溶体氧化物;而Mn O_2的加入可以降低氧化钌的结晶度。三组元相互配合降低离子扩散阻力,提高活性材料的利用率,从而提高Ti/Ru_(0.4)Mn_(0.6-x)Sn_xO_2电极材料的电荷存储能力。Ti/Ru_(0.4)Mn_(0.3)Sn_(0.3)O_2三元电极的比电容可达682 F/g,约为Ti/Ru O_2-Sn O_2和Ti/Ru O_2-Mn O_2二元氧化物电极的2~3倍。     

高比能量Ti/(Ir_(0.3)Sn_(0.7-x)Ce_x)O_2电极材料的制备及其电化学性能

采用热分解法在360℃制备Ti/(Ir0.3Sn(0.7-x)Cex)O2三元氧化物电极材料(0x0.5)。采用X射线衍射(XRD)、交流阻抗和循环伏安法分析成分对Ti/(Ir0.3Sn(0.7-x)Cex)O2电极材料的晶体结构和电化学性能的影响。结果表明:适量的Ce可降低氧化物涂层中金红石相的晶化程度,优化氧化物涂层的结构,并提高Ti/(Ir0.3Sn(0.7-x)Cex)O2电极材料的电容性能。当x=0.2时,Ti/(Ir0.3Sn0.5Ce0.2)O2电极的比电容达到414 F/g,约为Ti/Ir O2-Sn O2二元氧化物电极的3倍;该电容材料表现出很高的比能量特性,在4.97 k W/kg的高功率密度放电时,对应的能量密度达到82.88 W·h/kg。当x≥0.3时,随着Ce含量增大,氧化物涂层的导电性能和频率响应特性会遭到恶化,对电极的电容性能不利。因此,Ce的含量控制在0.2(摩尔分数)以内为宜。     

0.2Pb(Zn1/3Nb2/3)O3-0.8Pb(Zr0.5,Ti0.5)O3（1-x）(Ni51.5Mn25Ga23.5)x固溶体系磁电性能研究

采用传统的固相烧结法合成了0.2Pb(Zn1/3Nb2/3)O3-0.8Pb(Zr0.5,Ti0.5)O3(1-x)(Ni51.5Mn25Ga23.5)x复合体系陶瓷。XRD结果表明,随着Ni51.5Mn25Ga23.5(NMG)掺入,Ni51.5Mn25Ga23.5先溶于0.2Pb(Zn1/3Nb2/3)O3-0.8Pb(Zr0.5,Ti0.5)O3中,后NMG量超过5%不溶于复合体系中,使得0.2Pb(Zn1/3Nb2/3)O3-0.8Pb(Zr0.5,Ti0.5)O3的峰位向右偏移;铁电性能测试结果表明,0.2Pb(Zn1/3Nb2/3)O3-0.8Pb(Zr0.5,Ti0.5)O3(1-x)(Ni51.5Mn25Ga23.5)x复合体系陶瓷随着Ni51.5Mn25Ga23.5的掺入量的增加矫顽场E先降低后增加,剩余极化强度Pr逐渐降低,这与XRD的测试结果相一致;磁性测试结果表明,0.2Pb(Zn1/3Nb2/3)O3-0.8Pb(Zr0.5,Ti0.5)O3(1-x)(Ni51.5Mn25Ga23.5)x随着Ni51.5Mn25Ga23.5掺入量的增加,以独立相析出在复合体系中,剩余磁化强度Mr逐渐增大。     

La掺杂的SnO2-Sb中间层对钛基IrO2+Ta2O5电极性能的影响

目的改善Ti/IrO_2+Ta_2O_5涂层电极的析氧电催化性能。方法用热分解法在钛基材上制备了La掺杂的SnO_2-Sb中间层,并以此作为基体涂覆IrO_2+Ta_2O_5活性层,制备了Ti/SnO_2-Sb-La/IrO_2+Ta_2O_5涂层电极。采用扫描电子显微镜(SEM)、能量散射能谱(EDS)及X-射线衍射光谱(XRD)技术分别分析了中间层和活性层的表面形貌、元素组成及晶相结构。采用线性扫描伏安曲线(LSV)和强化寿命测试方法在硫酸溶液中分别研究了Ti/SnO_2-Sb-La/IrO_2+Ta_2O_5涂层电极的析氧电催化活性和使用稳定性。同时,考察了La的掺杂比例对Ti/SnO_2-Sb-La/IrO_2+Ta_2O_5电极强化寿命的影响。结果相对未掺杂La的中间层,掺杂La后的中间层表面裂纹减少,有更高的析氧过电位和更低的析氧电流密度。La掺杂对活性层的表面形貌和晶相结构基本没有影响,但电极的析氧电流密度有所提高。通过测试不同La掺杂比例涂层电极的强化寿命,发现La最佳掺杂比例为nLa:nSn=0.5:100。和未掺杂La涂层相比,La最佳掺杂比例涂层电极的强化寿命提高了22.8%。结论相对于未掺杂的Ti/SnO_2-Sb/IrO_2+Ta_2O_5电极,La掺杂后的Ti/SnO_2-Sb-La/IrO_2+Ta_2O_5涂层电极析氧电催化活性和强化寿命都得到改善。     

3d过渡金属掺杂对Bi0.8Ba0.2FeO3陶瓷多铁性能的影响研究

采用传统固相烧结法制备多铁性Bi_(0.8)Ba_(0.2)Fe_(0.9)M_(0.1)O_3(M=Cr,Mn,Ti)陶瓷。X射线衍射图谱(XRD)表明该材料为纯相菱形钙钛矿结构,属于R3c空间点群。铁电测试结果表明,Bi_(0.8)Ba_(0.2)Fe_(0.9)Ti_(0.1)O_3陶瓷具有室温下的最大剩余极化值(2Pr)为0.64μC/cm~2和低频时的最小介电常数值(ε)为140。同时,所有样品的介电常数和介电损耗均随着频率的增加而降低且在高频时趋于稳定。磁性测试结果表明,Bi_(0.8)Ba_(0.2)Fe_(0.9)Mn_(0.1)O_3陶瓷具有室温下的最大剩余磁化值(2Mr)为1.46(A·m~2)/kg。显著的磁极化前后P-E回线变化被观察到,这直接说明了多铁性Bi_(0.8)Ba_(0.2)Fe_(0.9)M_(0.1)O_3(M=Cr,Mn,Ti)陶瓷中存在磁电耦合效应,且Bi_(0.8)Ba_(0.2)Fe_(0.9)Cr_(0.1)O_3样品具有最显著的磁电耦合效应值为5.8 m J/cm~3。     

MeO掺杂AgSnO2电接触材料的结构与性能

采用机械合金化技术将不同用量的CuO或Fe_2O_3粉掺入银和SnO_2粉中制备Ag/SnO_2(x)-MeO(y)复合粉体,并辅以热压成型工艺制得Ag/SnO_2(x)-MeO(y)电接触材料。采用扫描电镜、X射线衍射仪、电阻测试仪、硬度计及拉伸试验机等测试仪器对材料的组织结构、物理和力学性能进行了表征。结果表明:随着掺杂剂用量的增加,Ag/SnO_2(x)-MeO(y)材料的密度逐渐降低,且CuO较Fe_2O_3更利于提高材料的导电性。2种掺杂剂均能显著改善Ag/SnO_2(x)-MeO(y)材料的塑性变形能力。Ag/SnO_2(11.2%)-CuO(0.8%)(也即CuO用量为0.8%)材料的电阻率达到最低值2.35μΩ·cm,延伸率约为9.1%,比Ag/SnO_2材料的延伸率提高近93.6%,综合性能最优。     

循环性能改善的La改性锂离子电池材料LiNi_(0.8-x)Co_(0.1)Mn_(0.1)La_xO_2（英文）

结合共沉淀法和高温固相法合成了一系列La掺杂的层状氧化物正极材料LiNi_(0.8-x)Co_(0.1)Mn_(0.1)La_xO_2(x=0,0.01,0.03),研究La对LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2材料的影响。通过XRD数据观察到了La_2Li_(0.5)Co_(0.5)O_4 相的生成,通过Rietveld精修软件计算了第二相的含量。电化学性能测试结果表明La掺杂之后材料的循环稳定性从74.3%上升到95.2%,而首次比容量从202 mA·h/g降低到了192 mA·h/g,循环稳定性的提高可以归因于新相的产生一方面消耗了材料中的杂质,另一方面粘附在颗粒表面保护材料不受电解液的腐蚀。CV测试结果表明与未掺杂的材料相比,掺杂后的样品电化学可逆性更好。     

十二烷基硫酸钠对IrO_2-Ta_2O_5/SnO_2-Sb-MnO_2/Ti电极电催化性能的影响

采用涂刷-热分解法制备不同浓度阴离子表面活性剂十二烷基硫酸钠(SDS)的IrO_2-Ta_2O_5/SnO_2-Sb-MnO_2/Ti电极。通过扫描电子显微镜(SEM)和X射线衍射仪(XRD)对其微观形貌及物相组成进行分析;应用循环伏安、极化等测试手段,表征制备电极的电催化活性。结果表明,适量添加十二烷基硫酸钠能够改善IrO_2-Ta_2O_5/SnO_2-Sb-MnO_2/Ti电极的微观形貌,提高电催化活性。在本实验条件下,SDS最佳添加量是1.6 g/L,结晶化度高达99.83%。利用苯酚电催化降解实验和强化寿命测试进一步考察所制电极的电催化活性与稳定性,结果显示,在电流密度15 mA/cm~2条件下电解180 min,SDS的加入使苯酚去除率由原来的68.5%提高到79.2%,COD去除率由60.1%提高到67.5%,电催化性能得到提升,电极强化寿命由52 h延长至68 h。     

Ti/Ir0.4Sn0.6O2电极材料的电容性能

为了得到高比电容的电极材料,采用热分解法制备了不同温度下Ti/Ir0.4Sn0.6O2电极材料。运用X射线衍射(XRD)、差热分析、扫描电镜(SEM)和循环伏安法(CV)分别测试了该材料的晶体结构、表面形貌和电化学特性。结果表明:涂层的晶化温度高于360℃。320℃退火的电极表面有很多白色小颗粒析出,其活性氧化物较多。比电容受热处理影响较大,在280℃时电容值很小,可逆性低,320℃退火的电极比电容为454 F/g。该电极随着充放电循环次数的增加,比电容增加,经过9000次循环后,比电容才开始下降,经历10000次循环充放电后的比电容为493 F/g,比未经循环时还大10%。     

钛基锡锑氧化物电极掺杂改性及应用研究进展

电催化氧化水处理技术是近年来发展起来的一种有效处理难降解有机废水的方法,钛基锡锑氧化物涂层阳极(Ti/SnO_2-Sb)因其对有机污染物具有较高的电化学氧化活性而受到关注。综述了稀土金属、非稀土金属、碳纳米管(CNTs)等物质掺杂改性Ti/SnO_2-Sb电极的研究进展。简述了掺杂剂影响Ti/SnO_2-Sb电极电催化活性、电流效率和电极寿命的作用机理;介绍了Ti/SnO_2-Sb及其改性电极降解有机污染物的应用研究情况;展望了今后Ti/SnO_2-Sb电极涂层掺杂改性及应用研究值得关注的方向。     

Al2O3包覆LiNi0.03Co0.05Mn1.92O4正极材料的制备及其电化学性能

以Al(NO3)3?9H2O为包覆原料,通过燃烧法制备得到LiNi0.03Co0.05Mn1.92O4@Al2O3正极材料。通过X射线衍射(XRD),场发射扫描电子显微镜(FESEM)和透射电镜(TEM)等表征手段对材料的结构和形貌进行分析,并通过恒电流充放电、循环伏安(CV)、交流阻抗(EIS)等测试分析材料的电化学性能。结果表明,Al2O3包覆没有改变LiNi0.03Co0.05Mn1.92O4的尖晶石型结构,包覆层厚度约10.6nm。LiNi0.03Co0.05Mn1.92O4@Al2O3正极材料电化学性能得到了明显改善,1 C和10 C倍率下初始放电比容量分别为119.9 mAh?g-1和106.3 mAh?g-1,充放电循环500次后容量保持率分别为88.4%和78.2%,而未包覆的LiNi0.03Co0.05Mn1.92O4在1 C和10 C倍率下初始放电比容量分别为121.2 mAh?g-1和104.0 mAh?g-1,500次循环后容量保持率分别为84.1%和67.6%。LiNi0.03Co0.05Mn1.92O4@Al2O3活化能为32.92 kJ?mol-1,而未包覆材料的活化能为36.24 kJ?mol-1,包覆有效降低了材料Li+扩散所需克服的能垒,提高了材料的电化学性能。     

In-situ TiB2 and Al2O3 formation by DC plasma spraying

In-situ plasma spraying (IPS) is a promising process to fabricate composite coatings with in-situ formed thermodynamically stable phases. In the present study, mechanically alloyed Al-12Si, B₂O₃ and TiO₂ powder was deposited onto an aluminum substrate using atmospheric plasma spraying (APS). It has been observed that, during the coating process, TiB₂ and Al₂O₃ are in-situ formed through the reaction between starting powders and finely dispersed in hypereutectic Al-Si matrix alloy. Also, obtained results demonstrate that in-situ reaction intensity strongly depends on spray conditions.     

Fe2O3-CaO-TiO2 体系下铁酸钙的合成过程及TiO2 和CaTiO3 的影响

为了确定高钛型钒钛磁铁矿烧结过程中铁酸钙的生成是受TiO₂还是TiO₂和CaO形成的CaTiO₃影响,首先利用Fe₂O₃和CaO的纯试剂合成了铁酸钙,并研究了TiO₂和CaTiO₃对钛铁酸钙 （FCT） 形成的影响。在Factsage 7.0软件进行热力学计算的基础上,通过在空气气氛下进行烧结,获得了在1023~1423 K温度范围内、不同烧结时间的不同样品。通过X射线衍射和扫描电镜-能谱分析等表征手段,对烧结样品的物相转变和微观结构变化进行了表征。发现FCT的形成过程主要分为2个阶段：前一阶段为1023~1223 K温度范围内Fe₂O₃与CaO之间的反应,合成产物为Ca₂Fe₂O₅,反应方程式为“Fe₂O₃(s)+ 2CaO(s)= Ca₂Fe₂O₅(s)”;后一阶段为1223~1423 K温度范围内Ca₂Fe₂O₅和Fe₂O₃的反应,主要产物为CaFe₂O₄,反应为“Ca₂Fe₂O₅(s)+ Fe₂O₃(s)= 2CaFe₂O₄(s)”,该阶段尤其是温度为1423 K时,反应速率显著加快,随温度的升高CaTiO₃显著增加。然而,Ti元素在铁酸钙中的固溶很难实现,TiO₂与铁酸钙之间的反应不是形成FCT的有效途径。随着保温时间的延长,CaTiO₃和FCT相界中Fe元素含量增加。FCT主要是通过Fe组分在CaTiO₃中固溶形成的,主要反应是“Fe₂O₃+CaTiO₃(s)=FCT(s)”。     

Effects of K2O-Li2O doping on surface and catalytic properties of Fe2O3/Cr2O3 system

The effects of K₂O and Li₂O-doping (0.5, 0.75 and 1.5 mol%) of Fe₂O₃/Cr₂O₃ system on its surface and the catalytic properties were investigated. Pure and differently doped solids were calcined in air at 400-600 °C. The formula of the un-doped calcined solid was 0.85Fe₂O₃:0.15Cr₂O₃. The techniques employed were TGA, DTA, XRD, N₂ adsorption at −196 °C and catalytic oxidation of CO oxidation by O₂ at 200-300 °C. The results revealed that DTA curves of pure mixed solids consisted of one endothermic peak and two exothermic peaks. Pure and doped mixed solids calcined at 400 °C are amorphous in nature and turned to α-Fe₂O₃ upon heating at 500 and 600 °C. K₂O and Li₂O doping conducted at 500 or 600 °C modified the degree of crystallinity and crystallite size of all phases present which consisted of a mixture of nanocrystalline α- and γ-Fe₂O₃ together with K₂FeO₄ and LiFe₅O₈ phases. However, the heavily Li₂O-doped sample consisted only of LiFe₅O₈ phase. The specific surface area of the system investigated decreased to an extent proportional to the amount of K₂O and Li₂O added. On the other hand, the catalytic activity was found to increase by increasing the amount of K₂O and Li₂O added. The maximum increase in the catalytic activity, expressed as the reaction rate constant (k) measured at 200 °C, attained 30.8% and 26.5% for K₂O and Li₂O doping, respectively. The doping process did not modify the activation energy of the catalyzed reaction but rather increased the concentration of the active sites without changing their energetic nature.     

成分配比对Ti/IrO2-Ta2O5电极电容性能影响

摘要：采用低温热分解法制备了Ti基IrO2-Ta2O5氧化物涂层电极。通过X射线衍射(XRD),循环伏安曲线,交流阻抗谱,恒流充放电等测试方法分析了Ta含量对IrO2-Ta2O5氧化物涂层组织结构及电容性能的影响。结果表明,Ta2O5可抑制IrO2的晶化程度。随涂层中Ta含量增加,晶化度降低。当Ta含量为60mol%时,IrO2-Ta2O5电极的结晶度为6.4%,具有较小的电荷转移电阻和最高的比电容（239.2F/g）,比IrO2电极比电容(54.1F/g)提高了近4倍。     

Preparation and characteristic of spherical Li3V2(PO4)3

Spherical Li₃V₂(PO₄)₃ was synthesized by using N₂H₄ as reducer. The products were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that single-phase, spherical and well-dispersed Li₃V₂(PO₄)₃ has been successfully synthesized in our experimental process. Electrochemical behaviors have been characterized by charge/discharge measurements. The initial discharge capacities of Li₃V₂(PO₄)₃ were 123 mAh g⁻¹ in the voltage range of 3.0–4.3 V and 132 mAh g⁻¹ in the voltage range of 3.0–4.8 V.     

CuInSe2 nano-crystallite reaction kinetics using solid state reaction from Cu2Se and In2Se3 powders

The reaction mechanism and CuInSe₂ formation kinetics using a solid state reaction from Cu₂Se and In₂Se₃ powders synthesized using a heating up process were investigated using X-ray diffractomy (XRD) and transmission electron microscopy (TEM). It was observed that the CuInSe₂ phase increased gradually, accompanied with a decrease in γ-In₂Se₃ with no intermediate phase as the calcination temperature and soaking time were increased. The reaction kinetics was analyzed using the Avrami and polynomial kinetic model, suggesting that CuInSe₂ formation from Cu₂Se and In₂Se₃ powders follows a diffusion-controlled reaction with an apparent activation energy of about 122.5-182.3 kJ/mol. Cu₂Se and In₂Se₃ phases react and directly transform into CIS without the occurrence of any intermediate phase and the size of the newly formed CuInSe₂ crystallites was close to that of the Cu₂Se reactant particle based on the TEM results, which indicated that the solid reaction kinetics may be dominated by the diffusion of In³⁺ ions.     

La2O3含量对Al2O3/Cu基复合材料组织与性能的影响

以La₂O₃粉、Al粉、CuO粉为反应物原料、纯铜为基体,采用原位合成技术和近熔点铸造法制备颗粒增强Cu基复合材料,研究La₂O₃对Al-CuO体系制备的Cu基复合材料组织及性能的影响。结果表明：添加La₂O₃可获得纳米Al₂O₃颗粒,且弥散分布于Cu基体中,制备的材料组织更加细小、均匀,其材料的电导率及摩擦磨损性能明显提高。当添加0.6%wtLa₂O₃,复合材料的电导率达到90.2%IACS,磨损量达到最小,相比未添加La₂O₃,其导电率提高10.1%,磨损量减小36.6%。     

Degradation mechanism of long service life Ti/IrO2-Ta2O5 oxide anodes in sulphuric acid

Ageing performances of long service life Ti/70%IrO₂-30%Ta₂O₅ (at mole fraction) anodes prepared at 450 °C over the whole electrolysis time in H₂SO₄ solution have been investigated. It is showed that, the whole electrolysis processes of these anodes can be divided into three stages consisting of `active', `stable' and `de-active' regions. In the first two stages, the dissolution of coated oxides is dominated (with IrO<sub>2</sub> component preferential loss) which results in decreasing of apparent current for oxygen evolution and voltammetric charge. It is found that, in these two stages, the preferential orientations of (1 1 0) and (1 0 1) planes in IrO<sub>2</sub> rutile decreases with electrolysis time, and that of (0 0 2) plane increases, while the preferential orientations remain to be stabilized in the `de-active' region. Therefore, the loss mechanism of catalyst coatings in this region is changed. Electrochemical impedance spectroscopy measurement shows a slight increase in reaction resistance (R_ct) of oxide catalysts for oxygen evolution in the `de-active' region, while a sharp rise in totally physical impedance of the whole anode. According to the experimental results, a degradation mechanism of the Ti based anodes has been proposed by degradation of Ti/catalyst layer interface resulting from the dissolution and anodic oxidation of metal base alternatively.     

Synthesis and thermal conductivities of ZnIn2Te4 and CdIn2Te4 with defect-chalcopyrite structure

ZnIn₂Te₄ and CdIn₂Te₄ have a defect-chalcopyrite tetragonal crystal structure with structural vacancies. In order to investigate the effects of vacancies on the lattice thermal conductivity (κ_lat), single phase samples of ZnIn₂Te₄ and CdIn₂Te₄ were synthesized and their κ_lat values were examined in the temperature range from room temperature to 850 K. The κ_lat data for ZnIn₂Te₄ and CdIn₂Te₄ were compared with those of Zn- and Cd-series chalcopyrite compounds with no vacancies. The results revealed that the presence of vacancies alone in the defect-chalcopyrite structure does not result in effective phonon scattering.