LiPON薄膜结构与电化学性能研究

采用355nm脉冲激光沉积(PLD)法制备了室温离子电导率为1.6×10-6Scm的LiPON电解质薄膜。用X射线衍射(XRD)、扫描电子显微镜(SEM)、傅立叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)等方法对薄膜的结构和形貌进行表征,讨论了LiPON薄膜的电化学性能与其结构之间的关系。结果表明,该薄膜是一种无针孔、无裂缝、厚度均匀的非晶态结构。N元素插入到Li3PO4中,取代POP和PO3结构中的O使N与P成键形成PN=P或PNPP,增加了薄膜中的网状结构,从而提高了离子电导率。另外,随着N含量增大,LiPON薄膜的室温离子电导率增大。     

溶胶-凝胶法制备Li2O-Al2O3-SiO2微晶玻璃粉末

采用溶胶-凝胶法制备了Li2O-Al2O3-SiO2系玻璃粉末,利用X射线衍射(XRD)、红外光谱(IR)等手段研究了Li2O-Al2O3-SiO2系玻璃的晶化过程,探讨了热处理温度和时间对晶相形成及晶体粒径的影响.结果表明:玻璃在热处理650℃下开始析晶,在1150℃左右晶体生长基本完全.随着热处理温度的升高和热处理时间的增加,晶体粒径增大.     

稳定剂对Beta-Al2O3固体电解质性能影响

以Li2O、MgO和Li2O+MgO为稳定剂制备了beta-Al2O3固体电解质,并利用X射线衍射分析(XRD)、扫描电镜(SEM)和交流阻抗谱(EIS)等技术考察了稳定剂种类及含量对β"/β相的形成、显微结构和离子电导率的影响。研究表明,beta-Al2O3电解质中β"相的含量随稳定剂含量的增加而增加;但电解质的显微结构和离子导电性能随稳定剂的含量的增加呈现先优化后衰减,0.70%Li2O和3.80%(质量分数)MgO最佳。Li2O稳定剂对显微结构和离子导电性能的影响更为显著;MgO稳定剂能使β"/β相的合成温度低50℃;而Li2O+MgO稳定剂不易获得良好显微结构和离子导电性能的电解质材料。不同稳定剂作用的电解质的离子电导率由高到低依次为:Li2O>MgO>(Li2O+MgO)。     

O2/(O2+Ar)比对磁控溅射La-Sr-Mn-O薄膜沉积速率的影响

采用直流磁控溅射技术,在不同的O2/(O2 Ar)体积比条件下于Si(100)基片上沉积La-Sr-Mn-O薄膜,结合扫描电子显微分析研究了O2/(O2 Ar)比对薄膜沉积速率的影响.结果表明:薄膜厚度均匀,O2/(O2 Ar)比是影响薄膜沉积速率的重要因素.基体温度和溅射气压较高时,薄膜沉积速率随O2/(O2 Ar)比增加呈抛物线规律下降,O2/(O2 Ar)比由4.4%增加到45.6%,沉积速率减小量可达52.8%;基体温度和溅射气压较低时,薄膜沉积速率随O2/(O2 Ar)比增大呈指数规律下降.薄膜沉积速率下降是由于被溅射原子/离子与氧原子/离子的碰撞几率随氧气含量增加而增大,从而降低了被溅射粒子的能量,使到达基片的粒子数减少.     

脉冲激光沉积制备的HT-LiCoO2薄膜中Li离子表观扩散的研究

采用脉冲激光沉积(PLD)方法在镀Pt的Si衬底上制备了LiCoO2薄膜,运用XRD、Raman光谱、SEM和循环伏安等方法对其结构与电化学性能进行表征,在此基础上着重采用电位间歇滴定技术(PITT)对其Li离子表观扩散进行了分析.结果表明,600 ℃制备的LiCoO2薄膜为HT-LiCoO2相,呈柱状晶结构,平均晶粒尺寸在100 nm以下,结晶度高,并且具有明显的[001]择优取向,但少量缺Li.伏安循环曲线表明,该LiCoO2薄膜具有良好的电化学可逆性,但只在3.9 V(vs Li/Li )附近出现一对氧化还原峰.PITT测试表明,PLD方法制备的HT-LiCoO2薄膜的Li离子扩散系数在10-8-10-9cm2/s,与其它方法(如射频磁控溅射)制备的HT-LiCoO2薄膜相比,扩散系数高1-2个数量级;并且PLD方法制备的HT-LiCoO2薄膜中Li离子扩散系数与相变有关,在两相共存区,由于相界钉扎的作用,Li离子扩散系数比其它区域小1-2个数量级.     

衬底温度对CuCrO_2薄膜结构及光电性能的影响

采用射频磁控溅射方法,在石英衬底上制备CuCrO_2薄膜。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、紫外吸收光谱以及电导率的测定,表征不同衬底温度沉积薄膜样品的结构与光电性能。结果表明:薄膜的结晶度、可见光透过率与室温电导率均随衬底温度的升高而增大。衬底温度升高至923 K后,薄膜由非晶转变为具有铜铁矿结构的单相CuCrO_2。1023 K沉积的薄膜光电性能最佳,其平均可见光透过率为50%,室温电导率为0.33 S/cm。在近室温区(150～300 K),1023 K沉积薄膜导电规律符合半导体热激活模式,激活能为0.04 eV。     

热处理对V2O5纳米薄膜组织与性能的影响

用溶胶-凝胶技术结合旋涂法在硅基片上制备了V2O5纳米薄膜,对样品在空气中进行不同温度的热处理.用X射线衍射(XRD)、扫描电子显微镜(SEM)和FT-IR对V2O5薄膜进行了表征,研究了V2O5的生长过程和反应过程的机理及其微结构随温度的变化.结果表明,可以通过升高热处理温度来提高薄膜样品的结晶程度、颗粒尺寸及其均匀程度,并增强V2O5(001)晶面的取向性,当热处理温度升高至500℃时,样品由非晶薄膜转变为致密的棒状多晶薄膜.同时随着热处理温度的升高,样品中的V4 被氧化为V5 ,使薄膜样品结构发生了重排,V=O振动模式发生蓝移.     

ZrW2O8薄膜的制备及热膨胀性质

采用溶胶-凝胶技术结合退火工艺在Pt(111)/Ti/SiO2/Si(100)基片上制备ZrW2O8薄膜,并研究了退火温度、退火时间对薄膜的影响.利用X射线衍射(XRD)及扫描电镜(SEM)对薄膜的物相及表面形貌进行表征;利用变温XRD研究薄膜的热膨胀性能.薄膜的变温XRD结果表明,在室温～700℃温度范围内,随着温度的升高,(211)和(310)晶面间距变小,其热膨胀系数为负值,而(332)晶面间距随温度升高变大,显示出正膨胀性质.这表明ZrW2O8薄膜材料的热膨胀性能是各向异性的.     

溶胶-凝胶法合成超细锂快离子导体Li1.3Al0.3Ti1.7（PO4）3粉体及其表征

以Ti(OC4H9)4、Li(CH3COO).2H2O、Al(NO3).9H2O和NH4H2PO4为原料,采用溶胶-凝胶法合成Li1.3Al0.3Ti1.7(PO4)3粉体,并研究热处理温度对粉体结构的影响。通过X射线衍射仪(XRD)、扫描电镜(SEM)和电化学阻抗谱(EIS)对制备粉体的结构与性能进行表征。结果表明:溶胶凝胶法可合成纯相LATP粉体,降低热处理温度,且粉体结晶性良好,粒径小于1μm,室温下电导率为1.32×10-3 S/cm,673 K时电导率达到8.94×10-2 S/cm,473～673 K下活化能为31.55 kJ/mol。     

CuCr_(1-x)Mg_xO_2(0≤x≤0.09)薄膜的光电性能

采用射频磁控溅射方法,在石英衬底上制备Mg掺杂的CuCrO2薄膜。通过XRD、紫外吸收光谱及电学性能的测量表征该系列薄膜样品的结构与光电性能。结果表明:退火处理后所有薄膜样品的结晶性良好,均为3R型铜铁矿结构;薄膜的电导率随掺杂量的增加而增大。当x=0.09时,样品的室温电导率可达6.16×10-2S/cm,比未掺杂的CuCrO2提高近400倍,且霍耳测试表明所制备的薄膜为p型导电体。电导率随温度变化关系表明:薄膜样品在200～300K的温度范围内均很好地符合Arrhenius热激活规律;当x=0.09时,最低激活能仅为0.034eV。薄膜的可见光透过率与光学带隙宽度均随掺杂量的增加而减小。     

Fe-15Ce合金在H2-CO2、H2-H2S及H2-H2S-CO2气氛下的腐蚀

研究了600℃时Fe-15Ce合金在H2-CO2、H2-H2S及H2-H2S-CO2 3种气氛中的腐蚀行为，Fe-15Ce合金腐蚀后发生了Ce的内氧化或形成了复杂的腐蚀产物膜，而未出现Ce的选择性氧化或硫化，这主要是合金中存在着两相及Ce在Fe中极低的溶解度的结果。Fe-15Ce合金在本实验条件下的氧化-硫化腐蚀速度低于相同温度、压力下的纯硫化。     

用氢-氧取代氧-乙炔作焊接切割的必要性及可行性

阐述了用氢代乙炔的必要性．通过时HGQU2000／315火焰电孤焊割机的考察和试用证实了用氢代乙炔的可行性，比较了两种气体的性质并提出了使用特性差异和注意事项．提出了进一步探索的问题。     

Thermodynamics and phase diagrams in the binary systems Na2O-SiO2, Na2O-GeO2, Na2O-B2O3, Li2O-B2O3, CaO-B2O3, SrO-B2O3, and BaO-B2O3

We applied our model to the enthalpy of mixing data of the binary systems Na₂O-SiO₂, Na₂O-GeO₂, Na₂O-B₂O₃, Li₂O-B₂O₃, CaO-B₂O₃, SrO-B₂O₃, and BaO-B₂O₃. The most stable composition in the liquid, that is where the enthalpy of mixing is most negative, is with a metal-oxygen ratio of 4 to 3, for monovalent metals (Na and Li) and 3 to 4 for divalent metals (Ba and Ca) in liquid silicates or borates. The same applies to the CaO-SiO₂, CaO-Al₂O₃, PbO-B₂O₃, PbO-SiO₂, ZnO-B₂O₃, and ZnO-SiO₂ systems. The oxygen to metal ratio, its constant value in various types of systems, reflects and describes the structure of the liquid. Using the analyzed enthalpies of mixing data and the available phase diagrams, we calculated the enthalpies of formation of the various binary compounds. The results are in excellent agreement with data in the literature that were obtained from direct solid-solid calorimetry.     

IrO2-MnO2中间层Ti/RuO2-TiO2-SnO2电极制备及性能

通过热分解法制备了含IrO2-MnO2中间层Ti/RuO2-TiO2-SnO2电极,采用SEM、EDX、XRD、CV等检测方法对中间层进行表征,同时采用强化加速寿命试验对电极电化学稳定性进行表征。结果表明:450℃时前躯体完全氧化并形成固溶体,制备的中间层晶粒细小,表面结构致密,电化学孔隙率小。添加中间层使Ti/RuO2-TiO2-SnO2电极强化寿命由未加中间层的7.5h提高到995.8h,远高于国家标准20h。     

ACTIVITY OF La_2O_3 IN LIQUID La_2O_3-CaF_2 AND La_2O_3-CaF_2-CaO-SiO_2 SLAGS

用石墨为还原剂,将渣中La_2O_3还原入液态Sn,以测定1500℃下La_2O_3-CaF_2和La_2O_3-CaF_2-CaO-SiO_2渣中La_2O_3的活度.对La_2O_3-CaF_2系,并用Gibbs-Duhem积分法求得CaF_2的活度. 根据液态渣的离子结构模型,对上述二渣系中La_2O_3的活度数据进行了简单的讨论.     

Mechanoluminescence in BaSi2O2N2:Eu

Mechanoluminescence (ML), a general term for the phenomenon in which light emission occurs during any mechanical action on a solid, can be divided roughly into two classes: destructive ML and non-destructive ML. For practical use in high-end applications (e.g. pressure sensors), materials with non-destructive ML properties are preferred. This paper reports on the strong non-destructive ML in BaSi₂O₂N₂:Eu. When irradiated in advance with ultraviolet or blue light, this phosphor shows intense blue-green light emission upon mechanical stimulation such as friction or pressure. The ML has an emission band peaking at 498 nm, which is ～4 nm red-shifted compared to the steady-state photoluminescence. The origin of the ML is discussed and related to the persistent luminescence of BaSi₂O₂N₂:Eu. The same traps are responsible for both phenomena. Based on the occurrence of ML in this phosphor, we were able to show that the predominant crystallographic structure of BaSi₂O₂N₂:Eu belongs to space group Cmc2₁.     

氢分子在贮氢材料Li2MgN2H2表面的吸附与解离

采用第一性原理计算方法研究了Li-Mg-N-H体系贮氢材料的放氢产物Li2MgN2H2的吸氢反应过程中的过渡态、表面电子态密度和表面能。结果表明:氢分子在Li2MgN2H2低指数表面中最低能量(100)表面的Mg-Mg-Li穴位吸附位置能够形成最稳定的吸附结构并发生解离,氢分子吸附能为-0.1898eV,解离能约为0.84eV(81kJ/mol),表明该反应所需的反应活化能仍较高,吸氢反应速度缓慢。     

The Quasi-Ternary System Cu2Se-Ga2Se3-GeSe2

The quasi-ternary system Cu₂Se-Ga₂Se₃-GeSe₂ was investigated using the methods of differential thermal and x-ray analysis. An isothermal section at 770 K and a liquidus surface projection of the phase diagram were constructed. The existence of the quaternary phase CuGaGeSe₄, the boundaries of solid solutions ranges of the system compounds were established.     

High temperature corrosion of Fe-Cr-Mn-alloys in H2-H2S and H2-H2O-H2S gas mixtures

The sulfidation of Fe-20% Cr-30% Mn, Fe-25%Cr-20%Mn and Fe-25% Cr was studied at 700°C in H₂-H₂S and the oxidation and sulfidation in H₂-H₂O-H₂S after preoxidation in H₂-H₂O. The sulfidation rate is strongly increased for the Mn-containing alloys, layers of (Mn,Cr)S and (Mn,Fe)Cr₂S₄ are formed. Also the oxidation rate is enhanced compared to Fe-25% Cr by formation of MnCr₂O₄ instead of Cr₂O₃. The sulfidation after preoxidation leads to internal and external sulfidation of the Mn-containing alloys. With increasing oxygen pressure p(O₂) = 10^?26…10^?22 atm. of the H₂-H₂O-H₂S mixtures the sulfidation is suppressed, for the higher oxygen pressure 10^?23 and 10^?22 atm. fast oxidation prevails under formation of MnCr₂O₄. Manganese cannot increase the sulfidation resistance of alloys, in spite of the stability and low degree of disorder of its sulfide, since the mixed sulfide (Mn,Cr)S is formed which has a high degree of disorder, high diffusivities and high growth rate according to the doping effect of trivalent Cr³⁺.     

34Cr2Ni2Mo

正34Cr2Ni2Mo结构钢具有高的强度、韧度和良好的淬透性和抗过热的稳定性,但白点敏感性高,有回火脆性。焊接性较差,焊前需经高温预热,焊后需消除应力,经调质后使用。一般制作强度高、塑性好的重要零部件,渗氮处理后制作特殊性能要求的重要零件,如轴类、齿轮、紧固件等。