Al_(2)O_(3)在储能材料中的应用研究进展

Al_(2)O_(3)作为陶瓷材料、催化剂、催化剂载体及研磨磨料等有广泛的应用。因氧化铝具有优良的抗酸碱腐蚀性和力学等性能且热稳定性好、来源丰富,所以近年来逐渐开始应用在储能材料领域,进一步拓展了氧化铝的应用范围。主要针对氧化铝包覆后的二次储能电池正极材料、负极材料,以及改进隔膜的力学性能等方面进行研究。报道了近年来氧化铝在锂离子电池、钠离子电池、锂硫电池、电解液、隔膜方面的应用研究进展。

Modification of Nano-α-Al2O3 and Its Influence on the Surface Properties of Waterborne Polyurethane Resin Composite Passivation Films

Silane coupling agent KH560 was used to modify the surface of nano-α-Al2O3 in ethanol-aqueous solution with different proportions. The particle size of nano-α-Al2O3 was determined by nano-particle size analyzer, and the effects of nano-α-Al2O3 content, ethanol-aqueous solution ratio and KH560 dosage on the dispersion and particle size of nano-α-Al2O3 were investigated. The material structure before and after modification was determined by Fourier transform infrared spectroscopy (FTIR). Aqueous polyurethane resin and inorganic components are combined with modified nano-α-Al2O3 dispersion to form chromium-free passivation solution. The solution is coated on the galvanized sheet, the adhesion and surface hardness are tested, the bonding strength of the coating and the surface hardness of the substrate are discussed. The corrosion resistance and surface morphology of the matrix were investigated by electrochemical test, neutral salt spray test and scanning electron microscope test. The chromium-free passivation film formed after the modification of nano-α-Al2O3 increases the surface hardness of galvanized sheet by about 85%. The corrosion resistance of the film is better than that of a single polyurethane film. The results show that the surface hardness and corrosion resistance of polyurethane resin composite passivation film are significantly improved by the introduction of nano-α-Al2O3.

Fabrication of Gd_(2)O_(3)-doped CeO_(2)thin films through DC reactive sputtering and their application in solid oxide fuel cells

Physical vapor deposition(PVD)can be used to produce high-quality Gd_(2)O_(3)-doped CeO2(GDC)films.Among various PVD methods,reactive sputtering provides unique benefits,such as high deposition rates and easy upscaling for industrial applications.GDC thin films were successfully fabricated through reactive sputtering using a Gd_(0.2)Ce_(0.8)(at%)metallic target,and their application in solid oxide fuel cells,such as buffer layers between yttria-stabilized zirconia(YSZ)/La0.6Sr0.4Co0.2Fe0.8O_(3−δ)and as sublayers in the steel/coating system,was evaluated.First,the direct current(DC)reactive-sputtering behavior of the GdCe metallic target was determined.Then,the GDC films were deposited on NiO-YSZ/YSZ half-cells to investigate the influence of oxygen flow rate on the quality of annealed GDC films.The results demonstrated that reactive sputtering can be used to prepare thin and dense GDC buffer layers without high-temperature sintering.Furthermore,the cells with a sputtered GDC buffer layer showed better electrochemical performance than those with a screen-printed GDC buffer layer.In addition,the insertion of a GDC sublayer between the SUS441 interconnects and the Mn-Co spinel coatings contributed to the reduction of the oxidation rate for SUS441 at operating temperatures,according to the area-specific resistance tests.

CO_2 capture using dry TiO_2-doped Na_2CO_3/Al_2O_3 sorbents in a fluidized-bed reactor

Abstract： In order to improve the reactivity of Na2CO3/Al2O3 sorbent with CO2, a new sorbent showing high reactivity was developed by doping Na2CO3/Al2O3 with TiO2 using impregnation. Fourteen multi-cycle carbonation/regeneration tests of the sorbent were carried out in a fluidized-bed reactor and the sorbent was characterized by X-ray diffraction and nitrogen adsorption. It is confirmed that TiO2 shows a positive effect on the adsorption process of Na2CO3 and the reaction rate is observed to increase significantly, especially in the first 10 min. Moreover, TiO2 is stable within the temperature range of the process and no other Ti-compounds are detected. The carbonation products are NaHCO3 and Na5H3 （CO3 ）4. The surface area and the pore volume of the sorbent keep stable after 14 cycles. The Fourier transform infrared spectroscopy and the X-ray photoelectron spectroscopy are used to analyze the effect mechanism of TiO2 on CO2 adsorption process of Na2CO3/Al2O3.

纯铜组元对Al_(2)O_(3)弥散强化铜变形性能的影响

为改善Al_(2)O_(3)弥散强化铜的变形性能,通过向弥散强化铜中加入软质相纯铜组元,研究纯铜组元对弥散强化铜烧结坯变形性能的影响。对弥散铜烧结坯进行热压缩变形实验,获得了其不同热变形条件下的真应力应变曲线,建立了基于双曲正弦本构关系Arrhenius流变应力模型的本构方程,并计算获得热激活能值Q与应变速率敏感系数值m;对热挤压试样,进行室温性能检测和微观组织表征。结果表明:加入纯铜组元后,弥散铜烧结坯应力应变曲线峰值应力下降,曲线走势波动减弱,变形试样缺陷减少,热激活能Q降低,变形难度下降。应变速率较低时,纯铜组元的加入使得m值增加,弥散强化铜的塑性变好;应变速率较高时,纯铜组元的加入加剧基体软硬相不协调变形,m值降低,塑性变差。纯铜组元的加入使热挤压弥散铜的强化相浓度降低,硬度下降,导电率提升,晶粒变大。

Three-photon-excited fluorescence of Tb^(3+)-doped CaO-Al_2O_3-SiO_2 glass by femtosecond laser irradiation

A near infrared to visible blue, green, and red upconversion luminescence in a Tb^3＋-doped CaO-Al2O3-SiO2 glass was studied, which was excited using 800 nm femtosecond laser irradiation. The upconversion luminescence was attributed to ^5D3→^7F5, ^5D3→^7F4, ^5D3→^7F3, ^5D4→^7F6, ^5D4→^7F5, ^5D4→^7F4, and ^5D4→^7F3 transitions of Tb^3＋. The relationship between upconversion luminescence intensity and the pump power indicated that a three-photon simultaneous absorption process was dominant in this upconversion luminescence. The intense red, green, and blue upconversion luminescence of Tb^3＋-doped CaO-Al2O3-SiO2 glass may be potentially useful in developing three-dimensional display applications.

Er^(3+)单掺及Er^(3+)/Yb^(3+)共掺SiO_2-Al_2O_3-La_2O_3玻璃光谱性质研究

研究了单掺Er3+ 及Er3+ /Yb3+ 共掺SiO2 Al2 O3 La2 O3玻璃的光谱性质随稀土离子浓度变化规律 ,应用McCumber理论计算了玻璃在 1.5 3μm的发射截面及积分吸收截面 .结果表明 :在Er3+ 离子掺杂浓度相同时 ,玻璃在 980nm吸收截面与Yb3+ 掺杂浓度成反比 ;当样品中Yb3+ 离子掺杂浓度为 3.94× 10 2 0 cm- 3时 ,玻璃在 1.5 3μm的吸收截面和发射截面最大 ,在 1.4 0～ 1.60 μm积分吸收截面也最大 ;Er3+ /Yb3+ 共掺SiO2 Al2 O3 La2 O3玻璃在 1.5 3μm的荧光半高宽随Er3+ 掺杂浓度升高而增加 ,当Er3+ 离子掺杂浓度为 2 .4 1× 10 2 0 cm- 3 时 ,玻璃的荧光半高宽 (FWHM )达到 5 2 .5nm .

Er^(3+):Y_3Al_5O_(12)/ZnO复合物的制备及其光催化性能的研究

通过溶胶凝胶、水热法合成了上转换发光剂Er^(3+):Y_3Al_5O_(12)掺杂的ZnO复合物可见光催化剂,采用X射线衍射仪(XRD)和扫描电镜(SEM)进行表征.以甲基橙染料为研究对象,研究了Er^(3+):Y_3Al_5O_(12)/ZnO复合物在可见光照射的光催化活性.此外,还研究了焙烧温度、焙烧时间、可见光照射时间和强度、染料溶液初始浓度和催化剂的用量对甲基橙染料降解率的影响.结果表明,加入上转换发光剂Er^(3+):Y_3Al_5O_(12)有效提高了降解率,且催化剂的用量为1.00g/L时降解效果最好.

Er^(3+)：Y_3Al_5O_(12)/ZnS复合物的制备及其光催化活性

分别通过溶胶凝胶、水热法合成了上转换发光材料Er3+Y3Al5O12和Er3+Y3Al5O12/ZnS复合物,并采用XRD和SEM进行表征,研究了Er3+Y3Al5O12/ZnS在可见光照射下降解次甲基蓝的催化活性。讨论了Er3+Y3Al5O12掺杂量、可见光照射时间、光照强度、催化剂的量、处理温度和处理时间对降解率的影响,并且与单一ZnS可见光光催化性能进行了比较。结果表明,加入上转换发光材料Er3+Y3Al5O12后降解率大幅度增加,且它掺杂量为10%时对染料废水的降解效果最好。

Sol-gel法制备Er^(3+)-Yb^(3+)共掺杂Al_2O_3粉末光致发光特性

采用异丙醇铝 [Al(OC3H7) 3]为前驱体 ,溶胶 凝胶 (Sol gel)法制备Er3+ Yb3+共掺杂Al2 O3粉末 实验结果表明 :90 0℃烧结的粉末为固溶Er3+、Yb3+的γ (Al,Er,Yb) 2 O3相和少量θ (Al,Er,Yb) 2 O3相的混合物 Er3+ Yb3+共掺杂Al2 O3粉末具有中心波长为 1.5 33μm的光致发光 (PL)特性 1mol %Er3+和 1mol%Yb3+共掺杂的Al2 O3粉末的PL强度较 1mol %Er3+掺杂提高 2倍 ,半峰宽从 5 3nm增加到 6 3nm 随泵浦功率的提高 。

氮掺杂碳改性Ni/Al2O3催化剂的甲烷干重整反应性能研究

在甲烷干重整反应(DRM)中,常规浸渍法制备的Ni/Al2O3催化剂常因过多积炭导致催化剂失活,因此研究如何提高Ni/Al2O3催化剂的抗积炭能力具有重要意义。通过浸渍法和高温碳化法制备的氮掺杂碳表面修饰的Ni/Al2O3催化剂Ni/Al2O3@NC-3和Ni/Al2O3@NC-5(3和5分别代表多巴胺聚合时间为3 h和5 h)在DRM中表现出了较强的抗积炭性能。使用X射线衍射(XRD)、拉曼(Raman)光谱、X射线光电子能谱(XPS)、热重(TG)和扫描电镜(SEM)等表征手段对催化剂的结构和电性质进行了分析,并探讨了氮掺杂碳的引入对催化剂稳定性和抗积炭性能的影响。XPS结果表明,Ni/Al2O3@NC-3和Ni/Al2O3@NC-5催化剂中金属Ni与氮掺杂碳发生了电子相互作用,形成了催化惰性的Ni+物种,由此减缓了CH_(4)的裂解速率,进而有效地减少了积炭的产生。在经8 h活性测试后,Ni/Al2O3@NC-3催化剂的CH_(4)转化率和CO_(2)转化率分别维持在52.2%和62.3%,且反应后Ni/Al2O3@NC-3催化剂的积炭量仅为7%(质量分数,下同),远远低于Ni/Al2O3催化剂的积炭量(25%)。

新型蓝色长余辉发光材料Sr_2Al_6O_(11):Eu^(2+),Er^(3+)的微波合成

在微波场作用下,首次合成了蓝色长余辉发光材料Sr2Al6O11:Eu2+,Er3+,利用XRD对其进行晶相分析,用荧光光度计测其激发光谱和发射光谱及余辉衰减曲线,利用热释光剂量仪测定其热释光谱。结果表明:该产品为正交晶系,Pnnm空间群,a=2.191827nm,b=0.840857nm,c=0.488175nm,该产品激发和发射谱均为宽带谱,在270和340nm处有2个主激发峰,主发射峰位于460nm,Sr2Al6O11:Eu2+,Er3+的发光余辉可持续14h以上,Sr2Al6O11:Eu2+,Er3+中存在2个热释峰,一个位于49.1℃,另一个位于140℃左右。2个陷阱能级分别为0.585eV和0.806eV。

直流辉光放电质谱法测定高纯α-Al 2 O 3颗粒中16种杂质元素

采用高纯Ga作为辅助电极,通过考察取样量、放电参数对基体信号强度、信号稳定性、基体和Ga的信号比值的影响,建立了直流辉光放电质谱法(dc-GDMS)测定高纯α-Al_(2)O_(3)颗粒中的Li、Be、Na、Mg等16种杂质元素含量的分析方法。当选取3颗2 mm左右大小的α-Al_(2)O_(3)颗粒用Ga包裹,在1.6 mA/950 V的放电参数下,基体27 Al信号稳定,强度为3.2×10^(8) cps,Al、Ga的信号比约为1∶270。采用实验方法对α-Al_(2)O_(3)颗粒独立测定5次,相对标准偏差均在30%以内。为了验证Ga对α-Al_(2)O_(3)颗粒测定结果的影响,分别采用电感耦合等离子体发射光谱法(ICP-OES)和dc-GDMS法对易于消解的γ-Al_(2)O_(3)粉进行测定。对于dc-GDMS法,选择压在Ga上的γ-Al_(2)O_(3)粉直径约为4~5 mm,在同样的放电参数下,27 Al的信号强度为3.0×10^(9) cps,Al、Ga的信号比约为1∶29。γ-Al_(2)O_(3)粉的GDMS测定结果和ICP-OES基本一致。采用Ga作辅助电极测定α-Al_(2)O_(3)颗粒和γ-Al_(2)O_(3)粉的检出限均可达ng/g。

Enhancement of Activity of SnO_(2)-doped In_(2)O_(3)/Al_(2)O_(3) Catalyst for NO Reduction with Propene in the Presence of H_(2)O and SO_(2)

The novel bimetallic Sn-Im/Al2O3 catalysts prepared by three methods for NO reduction by propene were investigated. The results showed that the catalytic activity was enhanced significantly in the presence of H2O on sol-gel catalyst, and the maximum NO conversion increased from 46% to 92%, even in the presence of 100 ppm SO2, NO conversion was still 80%.

Crystallization and Luminescence Properties of Sm3＋-Doped SrO-Al2O3-SiO2 Glass-Ceramics

The Sm^（3＋）-doped SrO-Al2O3-SiO2（SAS） glass-ceramics with excellent luminescence properties were prepared by batch melting and heat treatment. The crystallization behavior and luminescent properties of the glass-ceramics were investigated by DTA, XRD, SEM and luminescence spectroscopy. The results indicate that the crystal phase precipitated in this system is monocelsian（SrAl2Si2O） and with the increase of nucleation/crystallization temperature, the crystallite increases from 66 % to 79 %. The Sm（3＋）-doped SAS glass-ceramics emit green, orange and red lights centered at 565, 605, 650 and 715 nm under the excitation of 475 nm blue light which can be assigned to the 4 G5/2→6 Hj/2（j=5, 7, 9, 11） transitions ofSm^（3＋）, respectively. Besides, by increasing the crystallization temperature or the concentration ofSm^（3＋）, the emission lights of the samples located at 565, 605 and 650 nm are intensified significantly. The present results demonstrate that theSm^（3＋）-doped SAS glassceramics are promising luminescence materials for white LED devices by fine controlling and combining of these three green, orange and red lights in appropriate proportion.

Methanol Steam Reforming over Na-Doped ZnO-Al2O3 Catalysts

In this study, the catalyst composition in binary ZnO-Al2O3 catalyst was initially evaluated and optimized for methanol steam reforming. Then different Na contents were loaded by an incipient wetness impregnation method onto the optimized ZnAl catalyst. It was found that the activity was greatly enhanced by the modification of Na, which depended on the Na content in the catalyst. The methanol conversion was 96% on a 0.1 Na/0.4 ZnAl catalyst (GHSV = 14,040 h-1, S/C = 1.4, 350°C), which was much higher with respect to a Na-free 0.4 ZnAl catalyst (74%). The remarkable improvement of activity was attributed to a weakening of the C-H bonds and clear of hydroxyl group by the Na dopant leading to an accelerated dehydrogenation of the reaction intermediates formed on ZnAl2O4 spinel surface and thus the overall reaction.

Er^(3+)单掺、Er^(3+)/Yb^(3+)共掺杂Ca_(12)Al_(14)O_(32)F_2的制备及上转换发光性质

利用高温固相法成功制备了Er^(3+)单掺、Er^(3+)/Yb^(3+)共掺杂Ca_(12)Al_(14)O_(32)F_2上转换发光样品。在980 nm激光激发下,Er^(3+)单掺和Er^(3+)/Yb^(3+)共掺杂样品均呈现出较强的绿光(528,549 nm)和较弱的红光(655 nm)发射,分别归因于Er^(3+)离子的~2H_(11/2),~4S_(3/2)→~4I_(15/2)和~4F_(9/2)→~4I_(15/2)能级跃迁。随着Er离子浓度的增加,单掺杂样品上转换发光强度先增大后减小,最佳掺杂浓度为0.8%。共掺杂Yb^(3+)后,Er^(3+)的发光强度明显增大。还原气氛下合成的样品上转换发光强度增大约两倍,可能和笼中阴离子基团变化有关。发光强度和激发光功率的关系表明所得上转换发射为双光子吸收过程,借助Er^(3+)-Yb^(3+)体系能级结构详细讨论了上转换发射的跃迁机制。

掺杂导致的Al_2O_3:Er^(3+)的荧光发射的增强效应

通过先沉淀后退火法合成了Al2O3:Er3+荧光粉,研究了980nm激光激发下Al2O3:Er3+荧光粉的光致发光性质。为了增强Al2O3:Er3+荧光粉的荧光强度,Ba2+,Ca2+,Sr2+,Mg2+四种离子被掺杂进入了这种荧光粉中。结果了发现,掺杂后的Al2O3:Er3+荧光粉的荧光强度大幅度增加。

Y^(3+)共掺杂对掺Er^(3+):Al_2O_3粉末光致发光的增强作用

采用非水性溶胶-凝胶法制备了Y3+共掺杂的掺Er3+:Al2O3粉末,Er3+浓度为0．1和1．0mol％,Er3+和Y3+浓度比为1:0-10．X射线衍射和光致发光(PL)光谱结果表明: 900℃烧结的掺0．1和1．0mol％Er3+:Al2O3粉末为具有非晶化特征的γ和θ混合相结构,非晶化趋势随Y3+共掺杂浓度增大而增加．掺0．1mol％Er3+:Al2O3粉末,PL光谱强度和半高宽随掺Y3+浓度增大无明显变化．掺1．0mol％Er3+:Al2O3粉末,PL光谱强度和半高宽随掺Y3+浓度增大而增加,10mol％Y3+共掺杂粉末的发光强度提高50倍,约为掺0．1mol％Er3+:Al2O3粉末的10倍,半高宽从77nm增至92nm．Y3+共掺杂对较高浓度掺Er3+:Al2O3粉末PL性能的增强作用归因于Y3+对Er3+在基体中的分散和配位结构多样性的提高．

Er^3+,Cr^3+共掺杂BaAl2Si2O8荧光粉的发光性质及能量传递

利用高温固相法合成BaAl2Si2O8:Cr^3+,Er^3+系列荧光粉,研究了Cr^3+和Er^3+掺杂对BaAl2Si2O8材料发光特性的影响.BaAl2Si2O8:Er^3+荧光样品在393 nm激发波长下只呈现出峰值为550 nm的绿色荧光,来源于2H11/2→4I15/2和4S3/2→4I15/2跃迁的叠加.BaAl2Si2O8:Cr^3+荧光样品在550 nm激发波长下呈现峰值为694 nm的红色荧光,来源于2E→4A2的跃迁.在共掺杂样品BaAl2Si2O8:Cr^3+,Er^3+中,用Cr^3+激发峰的凹槽处380 nm作为激发光,得到的发射峰不仅有Er^3+的发射峰位,还有Cr^3+的发射峰位,说明两个离子之间可能存在辐射能量传递;对共掺杂BaAl2Si2O8:1%Cr^3+,x%Er^3+样品的荧光光谱进行测试,随着x的增加,Cr^3+的激发和发射光谱强度均有所增加,并且当x=0.5时,光谱强度是原来的4倍.另外,当固定Cr^3+的浓度时,随着Er^3+的浓度增加,Cr^3+的荧光寿命逐渐增加;当固定Er^3+的浓度时,随着Cr^3+的浓度增加,Er^3+的荧光寿命逐渐减小.这些现象表明了Er^3+和Cr^3+之间存在共振能量传递,通过理论计算得到Er^3+和Cr^3+之间的能量临界距离为4.5 nm,属于电偶极-电偶极相互作用.