室温快离子导体Rb4Cu16I7Cl13的电导率和热容研究

在-170-100℃的温度范围内,研究了室温快离子导体Rb₄Cu₁₆I₇Cl₁₃的电导率和热容随温度的变化,结果表明该材料在-50℃和-107℃附近各有一个二级相变存在。 关键词：     

流体静压力下快离子导体Rb4Cu16I7Cl13离子电导的研究

在流体静压力为0.5—11.6kbar,温度-80—80℃范围内,测量了Rb₄Cu₁₆I₇Cl₁₃多晶粉末“松散”样品和“致密”样品的离子电导。“松散”样品电导与压力的关系表明,在4.0—5.0kbar附近,电导存在极大值;“致密”样品电导随压力单调下降。在一定压力下,“致密”样品电导率随温度变化的趋势与常压结果相同,压力对Rb₄Cu₁₆I₇Cl_关键词：     

四氯乙烯的同步辐射光电离研究

利用VUV同步辐射光源和反射式飞行时间质谱仪，在超声冷却条件下对四氯乙烯(C₂Cl₄)进行了光电离研究，通过测量各离子的光电离效率(PIE)曲线，得到了C₂Cl₄的电离势IP(C₂Cl₄) =(9.36±0.05)eV及C₂Cl₄光解离碎片离子C₂Cl₃⁺，C_{关键词： 真空紫外光电离 离子出现势 电离势 四氯乙烯}     

Sm0.9Sr0.1AlO3-δ钙钛矿氧化物的固相反应合成和电学性能

用固相反应法制备了Sm_0.9Sr_0.1AlO_3-δ钙钛矿氧化物陶瓷.通过XRD,SEM和交流复阻抗谱以及氧浓差电池方法研究了样品的物相结构、微观形貌、电学性能及输运机理.结果表明,在1650℃烧结时,可以制备出单相的具有四方钙钛矿结构的氧化物Sm_0.9Sr_0.1AlO_3-δ;1650℃烧结16 h时的Sm_0.9Sr_0.1AlO_3-δ样品具有最高的相对密度和电导率,其值分别为96.7%和1.3×10^-2S/cm(900℃),比未掺杂的SmAlO₃的电导率大4个数量级左右,高温区电导活化能(T>670℃)小于低温区电导活化能(T<670℃);Sm_0.9Sr_0.1AlO_3-δ在空气气氛中是一个氧离子和电子空穴的混合导体,氧离子迁移数在0.7左右,并随温度升高逐渐增加,氧离子电导活化能(0.95eV)大于空穴电导活化能(0.84eV),900℃时氧离子电导率为9.65×10^-3S/cm. 关键词： 3')" href="#">SmAlO₃ 氧离子导电性 混合导体 活化能     

Rb掺杂C60单晶的相衍变和电子态

在C₆₀单晶超高真空解理面上制备C₆₀的Rb填隙化合物薄膜.用同步辐射光电子能谱研究了相衍变过程.观察到对应于固溶相、Rb₁C₆₀和Rb₃C₆₀的电子态密度分布.当数纳米厚Rb₃C₆₀薄膜在C₆₀单晶（111）解理面形成后，室温条件下进一步沉积Rb至样品表面不产生fcc到bct或bcc结构相变.C_{60 关键词： 4}C₆₀和Rb₅C₆₀吸附相')" href="#">金属性Rb₄C₆₀和Rb₅C₆₀吸附相 60单晶')" href="#">C₆₀单晶 相衍变 同步辐射光电子能谱     

铁基非晶合金磁致伸缩的温度效应

本文研究了Fe_80-xCu_xSi₅B₁₅,(Fe_1-xCo_x)₈₂Cu_0.4Si_4.4B_13.2两系列非晶合金的磁致伸缩系数λ₄随温度T的变化关系,温度范围分别为室温至非晶态居里点和室温至晶在居里点。分析了Fe基非晶合金随温度变化所产生的结构变化,并讨论了其磁致伸缩的单离子微观机制。 关键词：     

聚合物纳米复合电解质(PEO)8-ZnO-LiClO4微结构及电导率研究

以聚氧化乙烯(PEO)为基质,成功制备出纳米ZnO掺杂的(PEO)₈-ZnO-LiClO₄离子导电聚合物电解质,并利用多种实验技术,包括扫描电子显微镜、X射线衍射(XRD)、傅里叶变换红外光谱和正电子湮没寿命谱(PALS),系统地研究了纳米ZnO与基质间相互作用及其对聚合物链段运动、纳米尺度自由体积、离子输运和复合电解质电导率的影响.实验结果发现,纳米ZnO的掺杂使聚合物电解质的离子电导率得到了大幅度提高,当ZnO与PEO质量比为6%时达到最大,(PEO)₈-ZnO-LiClO₄的电导率为1.82×10^-4 S ·cm^-1,比(PEO)₈-LiClO₄的电导率(6.58×10^-5 S ·cm^-1)提高了大约一个数量级.XRD结果显示,纳米ZnO的加入降低了PEO的结晶性,增加了锂离子传输的非晶相,从而提高了电导率.离散PALS测量结果表明,随着纳米ZnO的加入,复合电解质的自由体积、浓度和相对自由体积分数f_r均增加.连续PALS分析揭示了自由体积的分布由一个峰劈裂成两个峰,表明纳米ZnO的掺杂对聚合物的微结构有很大影响.基于实验测量的f_r和离子电导率,研究了离子导电机理.研究发现, f_r与电导率之间存在一个直接关系,即f_r越大,越有利于锂离子的传输,导致电导率越大.这个结果支持聚合物电解质导电的自由体积理论. 关键词： 正电子湮没寿命谱 聚合物纳米复合电解质 离子电导率 自由体积     

XAFS和XRD研究高能球磨对Fe70Cu30合金结构的影响

利用XRD和XAFS方法研究机械合金化Fe₇₀Cu₃₀二元金属合金随球磨时间的结构变化.XRD结果表明，球磨2 h后，部分金属Fe与Cu生成Fe-Cu合金；球磨20h后，金属Fe与Cu已完全合金化生成Fe-Cu合金，并只在2θ=44°处出现一个宽化的弱衍射峰，认为是在球磨20h后的Fe₇₀Cu₃₀合金中共存着fcc和bcc结构的Fe-Cu合金相.XAFS结果进一步表明，在球磨的初始阶段(2h)，fcc结构的Cu颗粒的晶 关键词： XAFS XRD 70Cu₃₀合金')" href="#">Fe₇₀Cu₃₀合金 机械合金化     

Y1-xCaxBa2Cu3-xMxO7-δ (M=Fe,Ni)体系的超导电性

本文报道,通过对Y_1-xCa_xBa₂Cu_3-xMxO_7-δ(M=Fe,Ni)体系样品的晶体结构、氧含量、正常态电阻率与温度的关系,以及超导转变温度等测量,并与YBa₂Cu_3-xMxO_7-δ(M=Fe,Ni)体系进行比较,发现Y_1-xCa_xBa₂Cu_3-xFe_xO_7-δ体系的T_c显著地高于相应x值的YBa₂Cu_3-xFe_xO_7-δ体系,而Y_1-xCa_xBa₂Cu_3-xNi_xO_7-δ体系则相反,T_c低于仅Ni替代的体系,表明Ca和Fe同时替代时两者引起的载流子浓度(n_H)变化相互补偿,抑制了仅Fe替代时引起的n_H和T_c急剧下降;而作Ca和Ni同时替代时主要的不是两者引起载流子浓度变化的相互补偿,Ca和Ni替代效应之间的关联较弱。作者认为,对Y_1-xCa_xBa₂Cu_3-xFe_xO_7-δ体系属于CuO₂平面外的元素替代,这时载流子浓度是决定Tc的主要因素;而对Y_1-xCa_xBa₂Cu_3-xNi_xO_7-δ体系,由于Ni²⁺离子主要占据Cu(Ⅱ)位,它导致磁拆对效应,Ni²⁺离子的拆对效应是引起T_c下降的直接原因。 关键词：     

BiOCl1-xIx及BiOBr1-xIx固体溶液的制备、表征及性能研究

在太阳光照射下,利用半导体光催化去除污染物是最绿色、有效的方法之一,其核心问题是获得高效光催化剂。目前研究最多的光催化剂是TiO₂和ZnO等,但由于其禁带宽度大故不能充分利用太阳光,从而限制了其实际使用。除了对TiO₂等改性以改进其可见光催化活性外,开发其他材料作为光催化剂也是解决的重要途径。铋基化合物半导体由于原材料丰富、种类多、太阳光响应性好及优良的光催化活性而成为重要研究对象。其中卤氧铋系化合物[BiOX, X=Cl, Br, I]由于层状结构特点而具有良好的光催化活性,但单独使用时光催化效率较低。研究表明,BiOX间能通过形成固体溶液(即彼此呈分子分散的固体混合物)进一步改善其光催化降解污染物的能力。本文利用低温湿化学法,以Bi₂O₃为铋源,在醋酸溶液中加入一定比例的KI/KBr或KI/KCl水溶液,室温下反应0.5 h,分别得到片状结构的BiOCl_1-xI_x和BiOBr_1-xI_x固体溶液。X射线衍射(X-ray diffraction, XRD)分析结果表明,所合成的BiOCl_1-xI_x和BiOBr_1-xI_x样品结晶性良好,且能在x=0～1的范围内形成固体溶液。透射电子显微镜(transmission electron microscope, TEM)测得所制备的固体溶液呈不规则的薄片状。X射线光电子能谱(X-ray photoelectron spectroscopy, XPS)测试进一步证明了其表面元素组成及化学状态。紫外-可见漫反射光谱(diffuse reflectance spectroscopy, DRS)分析表明,随着碘元素含量的增加,固体溶液的吸收边界发生红移、禁带宽度减小,故可见光吸收能力增强、产生的载流子数目将增加。在可见光激发下对甲基橙(methyl orange, MO)降解的光催化性能研究表明,BiOCl_0.25I_0.75及BiOBr_0.25I_0.75拥有最高的光催化活性。循环实验表明,BiOCl_0.25I_0.75及BiOBr_0.25I_0.75都具有较高稳定性。光催化机理研究发现,这些卤氧铋样品光催化降解MO过程中的活性物种主要为空穴和超氧离子自由基。结合其能带结构,认为固体溶液的形成不但增加了可见光吸收能力,而且调变了其能带结构,相对于BiOI而言,固体溶液的形成降低了价带电位,提高了导带电位,因而增强了光生电子的还原能力及空穴的氧化能力,故催化性能提高。该工作的创新之处在于：采用的固体溶液制备方法,避免了高温水热法或加入表面活性剂等,而且所制备的BiOCl_1-xI_x和BiOBr_1-xI_x固体溶液,尤其是BiOCl_0.25I_0.75和BiOBr_0.25I_0.75,在可见光激发下对MO具有良好的降解能力,且催化剂的重复使用及稳定性良好,有望在环境治理中得到应用。     

Copper ion beam emission in solid electrolyte Rb4Cu16I6.5Cl13.5

Copper ion conducting solid electrolyte Rb$_{4}$Cu$_{16}$I$_{6.5}$Cl$_{13.5 }$ was prepared by means of mechano-chemical method. The structure and morphology of the powder was investigated by x-ray diffraction and scanning electron microscopy. The grain size was estimated to be 0.2-0.9 μm and the ionic conductivity at room temperature was approximately 0.206 S/cm. The solid electrolyte Rb$_{4}$Cu$_{16}$I$_{6.5}$Cl$_{13.5 }$ was exploited for copper ion beam generation. The copper ion emission current of several nA was successfully obtained at acceleration voltages of 15 kV and temperature of 197 $^\circ$C in vacuum of 2.1$\times10^{-4}$ Pa. A good linear correlation between the logarithmic ion current $(\log I)$ and the square root of the acceleration voltage ($U_{\rm acc}$) at high voltage range was obtained, suggesting the Schottky emission mechanism in the process of copper ion beam generation.     

CoSb3纳米热电材料的制备及热传输特性

以Sb，Co为起始原料，采用固相反应法合成了CoSb3.通过高能球磨制得CoSb3纳米粉末，用放电等离子烧结(SPS)方法制备出最小平均晶粒尺寸为150nm的块体材料.研究了晶粒尺寸与热传输性能之间的关系：CoSb3化合物结构纳米化对其晶格热导率κL有显著影响，当晶粒尺寸由微米尺度减小到纳米尺度，晶格热导率κL显著降低，但对载流子热导率κc的影响不甚显著.CoSb3化合物的热导率κ随晶粒尺寸的减小而降 低主要是由于晶格热导率κL随晶粒尺寸的减小而降低所致. 关键词： 纳米 Skutterudite 制备 热传输特性     

Oxygen-ion conducting electrolyte materials for solid oxide fuel cells

Oxygen-ion conducting solid electrolyte systems have been reviewed with specific emphasis on their use in solid oxide fuel cells. The relationships between phase assemblage, electrolyte stability and ionic conductivity have been discussed. The role of parameters such as sintering temperature and atmosphere which influence the segregation of impurities, present in the starting ceramic powders, at grain boundaries and at the external surface of the electrolyte compacts has been emphasised. The stability of various electrolyte materials in contact with other fuel cell components and in fuel environments has been discussed in detail. The ageing behaviour at fuel cell operating temperatures has been described. Data on ionic conductivity, mechanical and thermal properties have been presented for a number of electrolyte materials.     

锌掺杂固态电解质材料磷酸钛铝锂的制备及第一性原理研究

高安全性的固体锂离子电池是目前研究的热点之一,固态电解质是研究全固态电池的关键.磷酸钛铝锂固体电解质(LATP)具有良好的发展空间,因此采用高温固相法,制备锌掺杂LATP(LAZTP)固体电解质,通过XRD、SEM分析对比其物象和形貌特征,并对这两种材料压片进行阻抗分析,研究材料的电化学性能.基于密度泛函理论的第一性原理,研究LAZTP的能带结构和态密度与材料电化学性能的关系.结果表明:所掺杂锌的LATP材料,在球磨工艺下,与LATP相比衍射峰尖锐,材料结晶度良好,都为R-3C结构,LAZTP微观尺度下材料颗粒清晰,呈块状,孔隙均匀致密度较好,离子电导率相比较高,为1.9×10^-3S/cm,而制作的LATP的电导率为4.02x10^-4 S/cm,掺杂后的电导率明显高出一个数量级.计算得出的LATP能带带隙为0.163 eV和LAZTP能带带隙为0.05 eV,分态密度中Ti-s、Li-s、Al-s峰值尖锐,变化明显,表明掺杂锌后,材料明显提高了导电率和结构稳定性.     

Sensors for combustible gas components using modified single crystal zeolites

Single crystals of Heulandite- (HEU) type zeolites were characterized for phase homogeneity (XRD), morphology, chemical composition (SEM/EDX) and thermal stability (DTA). Afterwards the crystals were ion-exchanged against Ag and Cu in order to obtain defined starting materials for sensor applications. AC conductivity type sensors were constructed using ion-exchanged stilbite (HEU-type zeolite) as gas sensitive solid electrolyte with sputtered Au as electrode material. Temperature dependent conductivity measurements showed activation energies for the ionic motion between 0.54 and 0.76 eV. Ag-ion exchanged stilbites were applied as gas sensing materials in the temperature interval between 60 °C and 105 °C under defined H₂O concentrations and revealed stable signals with regard to different gaseous aliphatic components (mixtures with pure nitrogen or synthetic air). It could be shown that the sensor behaviour was affected by the polarity of the aliphatic molecules and their specific interaction with the ions and molecules of the channels within the zeolites lattice. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997     

The effect of composition,electron irradiation and quenching on ionic conductivity in a new solid polymer electrolyte: (PEG)<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>NH<Subscript>4</Subscript>I

We have prepared, characterized and investigated a new PEG-2000 based solid polymer electrolyte (PEG) _x NH₄I. Ionic conductivity measurements have been made as a function of salt concentration as well as temperature in the range 265–330 K. Selected compositions of the electrolyte were exposed to a beam of 8 MeV electrons to an accumulated dose of 10 kGy to study the effect on ionic conductivity. The electrolyte samples were also quenched at liquid nitrogen temperature and conductivity measurements were made. The ionic conductivity at room temperature exhibits a characteristic double peak for the composition x = 20 and 70. Both electron beam irradiation and quenching at low temperature have resulted in an increase in conductivity by 1–2 orders of magnitude. The enhancement of conductivity upon irradiation and quenching is interpreted as due to an increase in amorphous region and decrease in crystallinity of the electrolyte. DSC and proton NMR measurements also support this conclusion.      

Characterization of solid electrolytes prepared from ionic glass and ionic liquid for all-solid-state lithium batteries

Glassy solid electrolytes were prepared by combining the 50Li₂SO₄·50Li₃BO₃ (mol%) ionic glass and the 1-ethyl-3-methyl-imidazolium tetrafluoroborate ([EMI]BF₄) ionic liquid. High-energy ball milling was carried out for the mixture of the inorganic ionic glass and the organic ionic liquid. The ambient temperature conductivity of the glass electrolyte with 10 mol% [EMI]BF₄ was 10⁻⁴ S cm⁻¹, which was three orders of magnitude higher than that of the 50Li₂SO₄·50Li₃BO₃ glass. The addition of [EMI]BF₄ to the ionic glass decreased glass transition temperature (T_g) of the glass and the decrease of T_g is closely related to the enhancement of conductivity of the glass. Morphology and local structure of the glass electrolyte was characterized. The dissolution of an ionic liquid in an ionic glass with Li⁺ ion conductivity is a novel way to developing glass electrolytes for all-solid-state lithium secondary batteries.     

Lithium scandium phosphate-based electrolytes for solid state lithium rechargeable microbatteries

Li₃Sc₂(PO₄)₃ is a promising candidate for use as an electrolyte in solid state lithium rechargeable microbatteries due to its stability in air, ease of preparation, and resistance to dielectric breakdown. The room temperature ionic conductivity was optimized resulting in an increase of over two orders of magnitude to 3×10⁻⁶S/cm. The formation of Li₃(Sc_2−xM_x)(PO₄)₃, where M=Al³⁺ or Y³⁺, resulted in the decrease of porosity, greater sinterability, and considerable enhancement of the ionic conductivity. Yttrium substitutions enhanced the conductivity slightly while aluminum increased the room temperature ionic conductivity to 1.5×10⁻⁵S/cm for x=0.4. Preliminary electron beam evaporation of Li₃Sc₂(PO₄)₃ yielded amorphous thin films with ion ic conductivity as high as 5×10⁻⁵S/cm and a composition of Li_4.8Sc_1.4(PO₄)₃.     

Preparation of dense La<Subscript>0.9</Subscript>Sr<Subscript>0.1</Subscript>Ga<Subscript>0.8</Subscript>Mg<Subscript>0.2</Subscript>O<Subscript>3-δ</Subscript> with high ionic conductivity by solid-state synthesis

The results of a systematic investigation on the effects of processing steps, via solid-state reactions, on structural phase characteristics and ionic conductivity of La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-δ solid electrolyte are reported. The main purpose of this work is to establish an optimized route for obtaining good densification and high ionic conductivity of this solid electrolyte. Processing routes with three successive calcinations at 1250 °C followed by attrition milling (R1), and with two sequences of calcination at 1350 °C with intermediary attrition milling (R2) give rise to near full density at 1450 °C sintering temperature. The rate of grain growth is fast when the relative density reaches 95%. Elemental mapping reveals uniform distribution of the constituents in the matrix along with La₄Ga₂O₉, LaSrGa₃O₇ and sub-micrometer MgO grains at grain boundaries. The ionic conductivity of grains remains unchanged with the processing route and sintering profile. The blocking effect of charge carriers at grain boundaries decreases with increasing the dwell temperature.     

One-step fastest method of nanocrystalline CuAlS<Subscript>2</Subscript> chalcopyrite synthesis,and its nanostructure characterization

Nanocrystalline CuAlS₂ chalcopyrite has been mechanosynthesized at room temperature for the first time by ball milling the stoichiometric mixture of elemental of Cu, Al, and S powders under argon atmosphere. Initially, the CuAlS₂ phase is formed by solid state reaction of elemental powders within 15 min of milling and in the course of milling crystallite size decreases slowly to ~5 nm within 10 h of milling. Microstructure characterization and phase transformation kinetics of the elemental powders toward the chalcopyrite phase formation has been made by employing the Rietveld analysis using X-ray diffraction data of unmilled and ball-milled samples.