Sn_(0.95)Ta_(0.05)P_2O_7/PTFE复合电解质的制备及中温电性能

先采用固相法制备Sn0.95Ta0.05P2O7电解质样品,再与适量聚四氟乙烯(PTFE)进行复合合成了有机-无机复合电解质聚四氟乙烯/Sn0.95Ta0.05P2O7。XRD测试表明PTFE/Sn0.95Ta0.05P2O7复合电解质衍射图谱与焦磷酸锡的JCPDS标准衍射图谱卡立方相Sn P2O7(JCPDS 00-029-1352)相同,还可以看出复合后新增加了PTFE的衍射峰,表明Sn0.95Ta0.05P2O7和PTFE复合没有发生反应生成新物质。SEM图可以看出样品致密性良好。采用电化学工作站对样品的中温电性能(40~200℃)进行了研究。结果表明,Sn0.95Ta0.05P2O7/PTFE在160℃下,电导率达到最大值为:1.7×10-2S·cm-1。     

Zr_(0.92)Mg_(0.08)O_(1.92)和Zr_(0.92)Y_(0.08)O_(1.96)固体电解质的制备及性能

采用固相合成法在1 650℃分别合成了Zr0.92Mg0.08O1.92和Zr0.92Y0.08O1.962种固体电解质,其相对密度分别为96.19%和95.12%。XRD分析表明在Zr0.92Mg0.08O1.92和Zr0.92Y0.08O1.96固体电解质中均含有立方固溶体相,SEM分析表明2种材料微观结构致密。采用交流阻抗法分别测定了Zr0.92Mg0.08O1.92及Zr0.92Y0.08O1.96固体电解质在1 000~1 600℃的电导率。结果表明:随着温度的升高,Zr0.92Mg0.08O1.92固体电解质的电导率不断增大,但Zr0.92Y0.08O1.96的电导率在1 400℃时达到最大值(7.24×10—2 S/cm),随后降低;在1 000~1 450℃,Zr0.92Y0.08O1.96的电导率高于Zr0.92Mg0.08O1.92,在1 500~1 600℃,Zr0.92Mg0.08O1.92的电导率高于Zr0.92Y0.08O1.96。分析得到Zr0.92Mg0.08O1.92和Zr0.92Y0.08O1.96在1 000~1 450℃温度区间的电导激活能分别为1.61和0.20eV,在1 450~1 600℃温度区间的电导激活能分别为0.55和0.85eV。     

Mg_2Ni_(0.95)Sn_(0.05)-C_6H_6浆液体系储氢性能

研究了Mg_2Ni_(0.95)Sn_(0.05)和苯以及Mg_2Ni_(0.95)Sn_(0.05)氢化物与苯分别组成的浆液的储氢性能,通过研究不同温度下合金和氢化物对浆液吸氢速率的影响,发现氢化物比合金对浆液的反应速率的影响更为显著。温度对反应的影响特别明显,在反应釜中氢气压力为7 MPa,反应釜桨搅拌速度为500r·min~(-1),温度为513K时合金和氢化物分别和苯组成的浆液表现出最佳的吸氢性能,其最大吸氢量分别达到了5.87％(mass)和6.02％(mass)。添加Sn后的合金Mg_2Ni_(0.95)Sn_(0.05)对苯加氢到环己烷的转化有很好的选择性。     

新型复合阴极Sr_(0.95)Ti_(0.05)Co_(0.95)O_(3-δ)–Sm_(0.2)Ce_(0.8)O_(1.9)在中低温固体氧化物燃料电池中的性能

采用柠檬酸自蔓延燃烧法合成了Sr0.95Ti0.05Co0.95O3-δ(STC)阴极粉体和Sm0.2Ce0.8O1.9(SDC)电解质粉体,将STC与SDC粉体按质量比7:3混合得到复合阴极。通过X射线衍射(XRD)、直流四端子法和热膨胀仪表征了样品的化学相容性、电导率和热膨胀系数。XRD表明,STC在900℃能够得到立方纯钙钛矿结构,复合阴极STC-SDC在工作温度区间内具有很好的化学相容性;在650℃空气气氛下STC-SDC与SDC之间的界面极化阻抗仅为0.05Ω·cm2。制备了阳极支持型(Ni O-SDC│SDC│STC-SDC)单电池,在450~650℃范围内以湿润的H2(3%水蒸汽)为燃料气,空气为氧化剂测试了单电池的性能。结果表明:阳极支撑的单电池共烧1 350℃可以得到致密的电解质层和多孔的电极,而且650℃时单电池开路电压0.82V,最大输出功率为721 m W/cm2。结果预示,在以SDC为电解质的中低温固体氧化物燃料电池(IT-SOFC)中,STC-SDC是一个很有前途的复合阴极材料。     

溶胶凝胶法制备Ce_(0.8)Y_(0.15)M_(0.05)O_(2-δ)电解质材料及其性能研究

文章以Ce0.8Y0.15M0.05O2-δ(M=Fe、Co、Mg)为主要研究对象。通过红外、致密度分析、X射线衍射、扫描电镜、交流阻抗、热膨胀等测试方法对试样进行测试和分析,对实验得到的电解质粉及相应的电解质材料的性能进行表征。实验结果表明:溶胶-凝胶法经700℃煅烧成功制备出了单相立方萤石结构的超细粉末,具有良好的烧结活性。1300℃下烧结后相对密度达到97%以上。电导率的测试表明,电解质材料在中温范围有较高的电导率,其中,Ce0.8Y0.15Mg0.05O1.9在800℃时,电导率达到了0.0661 S/cm。     

La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3–δ)–Sm_(0.2)Ce_(0.8)O_(1.9)复合阴极的制备及性能表征

分别采用凝胶浇注法和甘氨酸–硝酸盐法制备La0.6Sr0.4Co0.2Fe0.8O3–δ(LSCF)粉体与Sm0.2Ce0.8O1.9(SDC)粉体,随后制备出不同比例的LSCF–SDC复合阴极。用X射线衍射分析粉体的化学稳定性,用扫描电子显微镜观察复合阴极的微观结构,在500～800℃范围内测量其热膨胀系数和电导率。采用丝网印刷法将LSCF–SDC涂覆在SDC电解质片上,在1100℃烧结4h。用交流阻抗法在600～800℃范围内测量不同成分的LSCF–SDC复合阴极和SDC电解质的交流阻抗谱。结果表明:LSCF和SDC粉体具有良好的化学相容性,烧结体具有多孔结构,LSCF–SDC复合阴极与SDC电解质可形成良好的接触界面。SDC的加入在降低阴极材料的热膨胀系数的同时还保持了其本身较高的电导率,在中温范围内,电导率达到500S/cm以上。复合阴极的极化电阻随着SDC的含量增加而减小,当SDC含量为30%时,复合阴极的极化电阻最小,在700℃空气中测试得到的界面电阻为0.32Ω·cm2。     

Pr的掺杂对固溶体Ce_(4.5)Gd_(1.5)MoO_(15-δ)电性能的影响

在固溶体Ce4.5 Gd1.5MoO15-δ体系中的Ce位引入少量Pr得新氧化物Ce4.5 Gd1.5-xPrxMoO15-δ(x=0.15).通过X射线粉末衍射(XRD)对氧化物结构进行分析,交流阻抗谱潮试电性能,讨论掺杂少量Pr对Ce4.5 Gd1.5 MoO15-δ电性能的影响.结果表明,少量Pr2的掺杂可降低晶界电阻,增加离子扩散通道,降低体系的总电导激活能和晶界电导激活能.提高氧化物的总电导率和晶界电导率.600℃时掺Pr材料的晶界电导牟为1.04×10-1 s/cm,高于未掺Pr材料的晶界电导率(5.27×10-4D/cm)约1倍.     

复合电解质SrCe0.9 Yb0.1 O3-α-LiCl-KCl的制备及其中温电性能研究

选择具有优良质子导电性的SrCe0.9 Yb0.1 O3-α与碱金属盐共熔体LiCl-KCl进行复合.制备复合电解质SrCe0.9 Yb0.1 O3-α-LiCl-KCl所用的温度(420℃)比制备SrCe0.9 Yb0.1 O3-α的温度(1500℃)显著降低.X射线衍射结果表明SrCe0.9 Yb0.1 O3-α和LiCl-KCl复合没有发生反应生成新物质.采用电化学工作站研究了单一SCYb电解质和复合SCYb-LK电解质在各种气氛中400~600℃下的电导率.结果表明,温度为600℃时,复合SCYb-LK电解质在湿润氮气气氛中的电导率为8.6×10-2 S·cm-1,复合SCYb-LK电解质的活化能远低于单一SCYb电解质.H2/O2燃料电池性能测试表明SrCe0.9 Yb0.1 O3-α-LiCl-KCl在600℃最大输出功率密度为113 mW·cm-2,是SrCe0.9 Yb0.1 O3-α在700℃相同条件下的7倍.     

(1-x)(Mg0.95Mn0.05)_2TiO_4-xCaTiO_3陶瓷的微波介电性能研究

采用传统固相法制备了(1-x)(Mg_0.95Mn_0.05)_2TiO_4-xCaTiO_3微波介质陶瓷,研究CaTiO_3添加量对陶瓷体系物相组成、显微结构以及微波介电性能的影响。XRD分析结果表明,陶瓷样品以(Mg_0.95Mn_0.05)_2TiO_4为主晶相,以CaTiO_3和MgTiO_3作为次晶相存在陶瓷样品中。另外发现添加CaTiO_3能增加陶瓷的致密度,并在1325~1400℃下都能促进陶瓷的烧结。当CaTiO_3的添加量为x=0.12时,复合陶瓷在1375℃烧结4 h时具有最佳的微波介电性能:介电常数ε_r=20.26,品质因数Q×f=35125.9 GHz,τ_f=+2.7×10~(-6)/℃。     

(Sn_(1-x),Ni_(2x))O_2纳米颗粒膜的制备及半导体性能

为提高SnO2的半导体性能,以分析纯SnCl2.2H2O和NiCl2.6H2O为主要原料,控制不同n(Ni2+)/n(Sn2+),利用溶胶凝胶-浸渍提拉法制备了(Sn1-x,Ni2x)O2纳米颗粒膜及半导体元件。用XRD、AFM对样品的结构、形貌进行了分析,并测试了(Sn1-x,Ni2x)O2元件的半导体性能。结果表明,(Sn1-x,Ni2x)O2纳米颗粒膜表面椭球形颗粒排列致密,尺寸约30 nm,(Sn1-x,Ni2x)O2为金红石型结构,但Ni2+代替了SnO2晶格中的部分Sn4+,使其晶胞参数a轴长平均减小0.000 4 nm,c轴长平均减小0.000 3 nm;随n(Ni2+)/n(Sn2+)由0.006增大到0.03,(Sn1-x,Ni2x)O2的晶粒尺寸由约45 nm减小至约18 nm;随温度由30℃上升至150℃,n型(Sn1-x,Ni2x)O2半导体元件的电阻约减小至其10%,而纯净SnO2元件的电阻仅约减小至其15%;随n(Ni2+)/n(Sn2+)的增大,离子化杂质散射增强,(Sn1-x,Ni2x)O2内部载流子迁移率下降,元件在150℃左右的电阻也由4.8 kΩ增大至12.1 MΩ,提高了元件的半导体性能。     

A vibrational study of phase transitions in Fe2P2O7 and Cr2P2O7 under high‐pressures

The vibrational properties of synthetic iron diphosphate (Fe₂P₂O₇) and chromium diphosphate (Cr₂P₂O₇) are studied under high‐pressure conditions between ~22 and ~30 GPa, respectively. Each compound's structural response to pressure and pressure‐induced phase transitions are characterized. The chromium‐bearing sample shows coalescence of infrared bands occurring near 6 and 17 GPa: these may be associated with increases in the local symmetry of the P₂O₇ group. The iron sample undergoes a first‐order phase transition near ~9 GPa, and a possible phase transition near 5.5 GPa. At 9 GPa, the initially single, strong symmetric PO₄ stretching mode splits into four modes, and the sole asymmetric PO₄ stretching mode splits into two bands. These changes indicate the presence of multiple tetrahedral environments within a larger volume unit cell, and the relative frequencies of the split vibrations indicate a P₂O₇ environment with a markedly narrowed P–O–P angle. The difference between the behavior of the iron and chromium compounds is probably generated by the smaller iron ion producing a discontinuous decrease in the P–O–P angle at lower pressures than in the analogous chromium compound. Our results demonstrate that the dimerized P₂O₇ group remains stable under compression to over 20‐30 GPa at 300 K.     

Facile Synthesis of BiOBr/Bi2Sn2O7 Heterojunction Photocatalysts with Improved Photocatalytic Activities

BiOBr/Bi₂Sn₂O₇ heterojunction photocatalysts were successfully synthesized by treating hydrothermal as‐prepared Bi₂Sn₂O₇ nanoparticles with hydrobromic acid (HBr). Partial Bi₂Sn₂O₇ nanoparticles reacted with HBr to form the sheet‐like BiOBr, and Bi₂Sn₂O₇ nanoparticles distributed evenly on BiOBr sheets. BiOBr/Bi₂Sn₂O₇ photocatalysts treated with different concentrations of HBr solution were successfully obtained, and their structures, morphologies, optical, and visible light photocatalytic properties were characterized by XRD, DRS, PL, SEM, and TEM. The experimental results showed that the BiOBr/Bi₂Sn₂O₇ photocatalysts showed improved photocatalytic activity under visible light irradiation than pure Bi₂Sn₂O₇. The sample treated with 0.08 mol/L HBr solution shows the best visible light photodegradation performance of rhodamine B. In addition, the active species and photocatalytic mechanism were discussed in detail.     

Li2O-CuO-P2O5玻璃的电性能

本文采用一种新的成形工艺制备20Li2O-30CuO-50P2O5(摩尔比)玻璃,并在玻璃转变温度之上对样品进行了不同时间的热处理后测试了其电性能。结果发现,随热处理时间的延长电导率会出现峰值,且所有样品电导率与温度之间的关系都能很好地遵从Arrhenius关系,结合SEM、XPS和XRD分析,对这一现象作出了初步的解释。     

A Sb‐doped SnP2O7 Solid Proton Conductor for Intermediate Temperature Fuel Cells

Sb‐doped SnP₂O₇ were prepared and characterised with XRD, FTIR, SEM and EIS. The preparation parameters were optimised taking into consideration the influence of H₃PO₄ content in the reactants and P_mO_n impurities. Conductivities of SnP₂O₇ with different Sb doping levels were studied from 100 to 300 °C in un‐humidified air. The conductivity of 20 mol‐% Sb‐doped SnP₂O₇ was greater than 0.1 S cm^–1 at 300 °C. The effect of heat treatment was identified as an important factor in the preparation of the proton conductors. The time dependence of the conductivity demonstrated Sb‐doped SnP₂O₇ as a promising intermediate temperature solid proton conductor.     

On comparison of luminescence properties of La2Zr2O7 and La2Hf2O7 nanoparticles

Unveiling the underlying mechanisms of properties of functional materials, including the luminescence differences among similar pyrochlores A₂B₂O₇, opens new gateways to select proper hosts for various optoelectronic applications by scientists and engineers. For example, although La₂Zr₂O₇ (LZO) and La₂Hf₂O₇ (LHO) pyrochlores have similar chemical compositional and crystallographic structural features, they demonstrate different luminescence properties both before and after doped with Eu³⁺ ions. Based on our earlier work, LHO-based nanophosphors display higher photo- and radioluminescence intensity, higher quantum efficiency, and longer excited state lifetime compared to LZO-based nanophosphors. Moreover, under electronic O²⁻→Zr⁴⁺/Hf⁴⁺ transition excitation at 306 nm, undoped LHO nanoparticles (NPs) have only violet blue emission, whereas LZO NPs show violet blue and red emissions. In this study, we have combined experimental and density functional theory (DFT) based theoretical calculation to explain the observed results. First, we calculated the density of state (DOS) based on DFT and studied the energetics of ionized oxygen vacancies in the band gaps of LZO and LHO theoretically, which explain their underlying luminescence difference. For Eu³⁺-doped NPs, we performed emission intensity and lifetime calculations and found that the LHOE NPs have higher host to dopant energy transfer efficiency than the LZOE NPs (59.3% vs 24.6%), which accounts for the optical performance superiority of the former over the latter. Moreover, by corroborating our experimental data with the DFT calculations, we suggest that the Eu³⁺ doping states in LHO present at exact energy position (both in majority and minority spin components) where oxygen defect states are located unlike those in LZO. Lastly, both the NPs show negligible photobleaching highlighting their potential for bioimaging applications. This current report provides a deeper understanding of the advantages of LHO over LZO as an advanced host for phosphors, scintillators, and fluoroimmunoassays.     

A PBI‐Sb0.2Sn0.8P2O7‐H3PO4 Composite Membrane for Intermediate Temperature Fuel Cells

Fine particles of a solid proton conductor Sb_0.2Sn_0.8P₂O₇ were incorporated in PBI‐H₃PO₄ membranes with 20 wt.%. In SEM figures, the Sb_0.2Sn_0.8P₂O₇ particles exhibited even and uniform distribution in the PBI‐Sb_0.2Sn_0.8P₂O₇ membrane. Influences of the immersing time and the concentration of H₃PO₄ solution for immersion on H₃PO₄ loading level were investigated. H₃PO₄ loading level was found an important factor on membrane conductivity. Incorporation of Sb_0.2Sn_0.8P₂O₇ in the PBI‐H₃PO₄ membrane resulted in greater membrane conductivities. In the single cell tests, the peak power density of the membrane electrode assembly (MEA) with the PBI‐Sb_0.2Sn_0.8P₂O₇‐H₃PO₄ membrane was also greater than that of a MEA with PBI‐H₃PO₄ membrane. One MEA using PBI‐Sb_0.2Sn_0.8P₂O₇‐H₃PO₄ membrane achieved a peak power density of 0.67 W cm^–2 at 175 °C with H₂/O₂ and exhibited satisfactory stability.     

细化颗粒固相法合成锂离子电池正极材料LiNi_(0.80)Co_(0.15)Al_(0.05)O_2及其结构和电化学性能研究

利用超细旋转盘式砂磨机细化颗粒固相烧结法,合成锂离子电池正极材料Li Ni0.80Co0.15Al0.05O2。原料经过砂磨后,混合均匀,粒径达到纳米级。根据塔曼定理,混合均匀的微小粒径可以在相同的烧结温度下,提高烧结的强度。SEM、XRD分别表征NCA材料的颗粒形貌和晶形结构。结果显示,通过细化颗粒烧结后的样品具有良好的形貌和层状结构。CV法测试样品的氧化还原性能,电池测试系统测试样品的电化学性能。测试结果显示,经过细化颗粒,在720℃合成的NCA材料具有良好的层状结构,018/110峰分裂明显。样品的电化学性能优良,0.2C下,首次放电容量达到182 m Ah?g?1,30次循环后容量保持率99.9%。1C下,首次放电容量153 m Ah?g?1,100次循环后容量保持率92.6%。     

Ba(Mg1/3Nb2/3)O3-Mg4Nb2O9复相陶瓷微波介电性能研究

采用传统固相法制备了(1?x)Ba(Mg1/3Nb2/3)O3?xMg4Nb2O9 [(1?x)BMN?xM4N2,x = 0.003 ~ 0.125] 微波介质陶瓷,研究了相结构、烧结性能与介电性能随 x 的变化规律。结果表明： BMN 与 M4N2 可以两相共存,且二者间存在有限固溶,BMN 的烧结温度及高温稳定性有所降 低。随着 x 的增大,介电常数 εr和谐振频率温度系数 τf逐渐减小,Q × f 值的变化易受到 BMN 有序参数 S 的影响,高度 1:2 有序的 x = 0.026 陶瓷获得了最大 Q × f 值 125000 GHz。综合来看, 在 1320°C 下保温 4 h 烧结的 x = 0.125 样品表现出最佳的微波介电性能：εr = 26.6,Q × f = 111000 GHz,τf = 5 ppm/ºC。