Microstructure–conductivity relationship of Na3Zr2(SiO4)2(PO4) ceramics

The ionic conductivity of solid electrolytes is dependent on synthesis and processing conditions, ie, powder properties, shaping parameters, sintering time (t_s), and sintering temperature (T_s). In this study, Na₃Zr₂(SiO₄)₂(PO₄) was sintered at 1200 and 1250°C for 0-10 hours and its microstructure and electrical performance were investigated by means of scanning electron microscopy and impedance spectroscopy. After sintering under all conditions, the sodium super-ionic conductor-type structure was formed along with ZrO₂ as a secondary phase. The microstructure investigation revealed a bimodal particle size distribution and grain growth at both T_s. The density of samples increased from 60% at 1200°C for 0 hours to 93% at 1250°C for 10 hours. The ionic conductivity of the samples increased with t_s due to densification and grain growth, ranging from 0.13 to 0.71 mS/cm, respectively. The corresponding equivalent circuit fitting for the impedance spectra revealed that grain boundary resistance is the prime factor contributing to the changing conductivity after sintering. The activation energy of the bulk conductivity (E_a,bulk) remained almost constant (0.26 eV) whereas the activation energy of the total conductivity (E_a) exhibited a decreasing trend from 0.37 to 0.30 eV for the samples with t_s = 0 and 10 hours, respectively—both sintered at 1250°C. In this study, the control of the grain boundaries improved the electrical conductivity by a factor of 6.     

Structure and physical properties of Ba(PO3)2–AlF3–BaSO4 fluoro-sulfo-phosphate glasses

Alkali-earth-metaphosphate-based fluoro-sulfo-phosphate M(PO₃)₂–AlF₃–MSO₄ (MPFS, M = Ca, Sr, Ba) glasses have been developed via simultaneously incorporating fluoride and sulfate into metaphosphate glass. Their glass-forming regions were efficiently determined under the guidance of thermodynamic calculation method. The physical and structural properties of BaPFS glass were investigated in detail. Furthermore, near-infrared spectroscopic properties of Er³⁺-doped BaPFS (Er–BaPFS) glass were studied. Physical parameters, such as Abbe's number ν_d (55-75) and nonlinear refractive index n₂ (1.17-1.86 × 10⁻¹³ esu), of BaPFS glass are strongly depended on P/F/S ratio. The structure of BaPFS glass gradually depolymerizes and tends to become multianionic when Ba(PO₃)₂ is substituted by AlF₃ and BaSO₄. Anion-substitution strategy effectively modulates the property and structure of glass, providing a scheme to derive glass materials. In addition, enhanced emission at ~1.5 μm has been observed from Er–BaPFS glass along with large emission cross section (5.0-5.5 × 10⁻²¹ cm²) and long lifetime (6.7-7.3 ms), resulting in large figure of merit (3.46-3.84 × 10⁻²³ cm²·s), which is a promising candidate for solid-state laser.     

NaTi2(PO4)3的合成及电化学性能测试

以Na_2CO_3、TiO_2和NH_4H_2PO_4为原料,采用球磨和高温烧结的方法合成了NaTi_2(PO_4)_3材料,研究发现烧结温度对于材料的生成和结晶性具有显著影响,烧结温度越高,所合成的NaTi_2(PO_4)_3相越纯,得到的产率也越高。测试了制备的NaTi_2(PO_4)_3材料作为钠离子电池负极材料的电化学性能,其比容量0.1 C倍率下可达到107 mAh/g。     

快速均匀沉淀法制备Zn3(PO4)2纳米微粒

采用快速均匀沉淀法在水相体系中制备Zn3(PO4)2纳米微粒。以H3PO4和Zn(NO3)2作为反应起始溶液，通过加入含表面活性剂聚乙二醇辛基苯基醚（OF）的冷氨水，制备出无团聚、粒度分布窄、粒径为40－50nm的球形Zn3(PO4)微粒。     

Cu-P-Zn3(PO4)2((ZnSiO3)纳米复合材料镀层的制备和性质

通过正交试验选择制备Cu-P-Zn3（PO4）2（ZnSiO）3纳米复合材料镀层的最佳溶液组成及条件，得到光亮，致密且孔隙率低的镀层。用扫描电子显微镜（SEM）观察其外貌：硬度仪测定其硬度：称重法测定其厚度：5％NaCl加速腐蚀试验、常温氧化试验、孔隙率试验等多种方法测定其耐腐蚀性能。结果表明：纳米微粒的存在提高了Cu-P化学镀层的耐腐蚀性能。     

NZP族磷酸盐晶体化合物NH4Zr2(PO4)3的水热合成

以(NH4)2HPO4为磷源,ZrO(NO3)2为锆源,用共沉淀法合成无定形前驱体,进一步采用水热晶化法制备出了NH4Zr2(PO4)3结晶化合物.研究了晶种、矿化剂(氟离子)添加量、水热合成温度和时间、pH值等对形成具有NaZr2P3O12(NZP)族晶体结构的化合物的影响,得到的最温和的水热晶化合成条件,即:按摩尔比n(F-)/n(ZrO2=1 HF引入HF作为矿化剂,添加占产物质量15%的晶种,在pH=1～5的酸性环境下,在50℃水热合成24h,可以得到结晶良好的单相NH4Zr2(PO4)3,用Brunauer-Emmett-Teller氮吸附法测定其比表面积为3.17m2/g,总孔容为0.00493mL/g.结果表明:所合成的具有三维网络状骨架结构的NZP族结晶化合物NH4Zr2(PO4)3因不具备类似微孔沸石分子筛的多孔性质,故更适合作为NZP族陶瓷的粉体材料而非分子筛催化材料.     

碳纳米管修饰NaTi2(PO4)3电极材料的制备及应用

本文采用溶胶-凝胶法制备复合材料,通过加入碳纳米管来改善其电导率。SEM和TEM分析表明,结晶良好的NaTi_2(PO_4)_3@C颗粒均匀地分散并嵌入碳纳米管中,复合材料由于碳层和碳纳米管构成的导电网络可以极大地促进电子/离子的传输。因此,所制备的电极在0.2C下可逆容量高达128.1 mAh·g~(-1),在10C下可逆容量高达94.3 mAh·g~(-1),循环性能优良,在2C下循环200次后容量保持率可达94.2%。从实验结果可以看出该材料应用前景广泛。     

Synthesis and lithium ionic conductivity of Li3−2x(In1−xZrx)2(PO4)3 (0≦x≦0·20)

Lithium ion conductors, Li_3−2x(In_1−xZr_x)₂(PO₄)₃ (0≦x≦0·20), were synthesized by a solid state reaction. A superionic conductive phase of Li₃In₂(PO₄)₃ was stabilized down to room temperature, assisted by the substitution of Zr⁴⁺ for In³⁺ sites of Li₃In₂(PO₄)₃. TG-DTA analysis indicated no phase transition in the samples with x superior to 0·05. The substituted samples showed much higher ionic conductivity by a couple of magnitude than that of Li₃In₂(PO₄)₃. In particular, the highest conductivity at room temperature was 1·42×10⁻⁵ Scm⁻¹ for Li_2·8(In_0·9Zr_0·1)₂(PO₄)₃. Thin films with the composition of Li_2·8(In_0·9Zr_0·1)₂(PO₄)₃ was prepared by a sol–gel method. A coating solution was made from lithium isopropoxide, indium isopropoxide, zirconium isopropoxide and diphosphorus pentaoxide. Well crystallized films were obtained on silicon dioxide and quartz glass substrates by dropping the coating solution, followed by firing over 873 K. In the temperatures above 473 K the lithium ionic conductivity of the film was slightly higher than that of sintered samples prepared by the solid state reaction at 1373 K.     

新型橙红色荧光粉KNaCa2(PO4)2∶Sm3+的发光性能

利用高温固相法合成了KNaCa2(PO4)2∶Sm3+系列橙红色荧光粉,并对其发光性能进行了研究.样品的激发光谱在402 nm有很强的发射带,与近紫外LED芯片匹配.在402nm近紫外光激发下,KNaCa2(PO4)2∶Sm3+的发射光谱由3个峰组成,发射峰值位于569、601和648nm处,分别归属于Sm3+的4G5/2→ 6HJ/2(J=5,7,9)跃迁.随着Sm3+掺量的增加,样品发光强度先增强后减弱,当Sm3+掺量为0.02 mol时发光强度达到最大,浓度猝灭机理为电偶极-电偶极相互作用.分析了不同Sm3+掺杂浓度样品的荧光衰减时间,并研究了电荷补偿剂Li+对样品发光强度的影响.样品KNaCa1.96(PO4)2∶0.02Sm3+,0.02Li+发射光谱(402nm激发)的积分强度是商用红色荧光粉Y2O3∶Eu3+发射光谱(253 nm激发)的1.5倍.     

Oxidative dehydrogenation of ethane and propane over magnesium–cobalt phosphates CoxMg3−x(PO4)2

The magnesium–cobalt phosphates Co_xMg_3–x(PO₄)₂ belonging to the olivine-type structure were synthesized by coprecipitation and then investigated in the oxidative dehydrogenation (ODH) of ethane and propane. The best yields, with the exception of Co_0.5Mg_2.5(PO₄)₂, were achieved with the compositions ranging between 1x2.5. Magnesium phosphate Mg₃(PO₄)₂ displayed no activity and pure cobalt phosphate Co₃(PO₄)₂ was found to be the less active component of the solid solution. Comparison of the catalysts performances showed that they all have similar activity in ethane and propane ODH, albeit, they are more selective in propylene than in ethylene production. The Co_xMg_3–x(PO₄)₂ solid solution was also studied, for characterization purposes, in butan-2-ol conversion. The samples presented acid–base properties due essentially to the (PO–H) groups but they do not bear conventional redox centers. All the catalysts were active at low temperatures in the alcohol dehydration. The dehydrogenation activity versus the phosphates composition displayed two maxima around x=1 and 2, respectively. Similar striking behavior was also observed in ethane and propane ODH. UV-visible investigations of Co_xMg_3–x(PO₄)₂ showed, in agreement with the XRD data, that the Co^{2 +} ions are distributed in the phosphate framework between six- and five-coordinated sites. The cobalt atoms in the five-coordinated sites Co(5) and their Co(5)–Co(5) interatomic distances were assumed to play the main role in the C–H bond activation and the appearance of maxima in the activity. Magnesium cations presumably intervene in acid–base properties of the samples and O₂ activation. Characterization of the samples showed that they do not undergo any noticeable transformation after the catalytic tests.     

NaTi2(PO4)3纳米晶的室温固相合成及表征

以Ti(SO4)2和Na3PO4·12H2O为原料,在表面活性剂聚乙二醇(PEG)-400的存在下,进行固相反应,然后将混合物在60 ℃下保温4 h, 接着用水洗去混合物中的可溶性无机盐并于100 ℃下干燥,即得纳米晶NaTi2(PO4)3 的前驱体,将前驱体煅烧可得NaTi2(PO4)3纳米晶.前驱体和它的煅烧产物通过TG/DTA,IR,XRD和UV-vis表征.结果表明,500 ℃下煅烧2 h得到的产物为无定形结构,700 ℃下煅烧2 h得到具有高结晶度的斜方NaTi2-(PO4)3[空间群R-3c(167)],其平均一次粒径为47 nm.前驱体及煅烧产物均具有强的紫外吸收能力.     

Li3PO4助熔剂添加对Li1.3Al0.3Ti1.7(PO4)3性质的影响研究

采用溶胶-凝胶法合成Li1.3Al0.3Ti1.7(PO4)3粉末,向Li1.3Al0.3Ti1.7(PO4)3粉末中添加不同摩尔分数的Li3PO4助熔剂烧结制备锂离子固体电解质Li1.3Al0.3Ti1.7(PO4)3烧结片。通过X射线衍射仪、扫描电子显微镜研究合成产物的结构与形貌,采用循环伏安及交流阻抗技术研究合成产物的氧化-还原电位、离子电导率和活化能。结果表明,添加与未添加Li3PO4助熔剂的Li1.3Al0.3Ti1.7(PO4)3烧结片具有相似的X射线衍射结果。添加Li3PO4的Li1.3Al0.3Ti1.7(PO4)3烧结片空隙率较小,更为致密。添加Li3PO4对Li1.3Al0.3Ti1.7(PO4)3的氧化-还原电位影响不大。在所有添加Li3PO4助熔剂的Li1.3Al0.3Ti1.7(PO4)3烧结片中,添加摩尔分数1%Li3PO4的烧结片具有最高的离子电导率6.15×10-4S.cm-1和最低的活化能0.314 2 eV。     

Co掺杂对Na3V2(PO4)2F3材料结构和电化学性能的影响

首次采用溶胶-凝胶法制备Co掺杂Na_3V_(2-x)Co_x(PO_4)_2F_3(x=0.00,0.05,0.1,0.2)钠离子电池正极材料。使用XRD、FE-SEM、恒流充放电和交流阻抗测试分析了Co掺杂对Na_3V_2(PO_4)_2F_3材料的结构和电化学性能的影响。结果表明,Co~(2+)取代V~(3+)可在Na_3V_2(PO_4)_2F_3晶格内产生V~(3+/4+)混合电价从而提高Na_3V_2(PO_4)_2F_3材料的电子电导率,具有更大离子半径的Co~(2+)替换V~(3+)可增大Na_3V_2(PO_4)_2F_3晶胞体积,扩宽钠离子传输通道,从而提高其离子电导率。此外,Co掺杂可有效减小Na_3V_2(PO_4)_2F_3电极的电荷转移阻抗。电化学测试结果表明,x=0.1时的Na_3V_(1.9)Co_(0.1)(PO_4)_2F_3电极展现出了最优异的电化学性能,0.1C时的首次放电比容量为111.3mAh·g~(-1),5C时首周可逆容量为91.9mAh·g~(-1),循环80次的容量保持率为70%。     

Influence of vanadium substitution on sintering behaviour of Pb3(VO4)2(1−x)(PO4)2x ceramics

Intermediate-stage sintering has been investigated in lead orthophosphovanadates Pb₃(VO₄)_2(1−x)(PO₄)_2x. It was found that rich-vanadium compounds such as Pb₃(VO₄)₂ and Pb₃(VO₄)_1.6(PO₄)_0.4 densify rapidly with important grain growth. For these compounds grain growth is controlled by grain boundaries and densification occurs by a mixed mechanism with lattice and grain boundary diffusion. For Pb₃(PO₄)₂, sintering mechanism supports a model of grain-boundary-controlled densification and grain growth is a surface diffusion-controlled pore drag mechanism. Moreover, the presence of phosphorus in compounds' formulae, tends to decrease the grain-boundary mobility, preventing pore-boundary separation. The kinetics analysis highlights the importance of vanadium substitution in modifying the diffusion coefficient of rate-limiting species.     

溶剂热法合成Li3V2(PO4)3的形貌及粒径控制研究

Li_3V_2(PO_4)_3因其突出的理论比容量和较高的工作电压,被认为是极具应用潜力的新一代锂离子电池正极材料之一。本实验以Li OH,NH_4H_2PO_4和NH_4VO_3为反应原料,通过溶剂热法合成Li_3V_2(PO_4)_3(LVP)正极材料。探讨了原料的添加顺序,溶剂的种类和比例,反应温度以及保温时间对LVP形貌和粒径的影响。利用扫描电镜观察其形貌和粒径,采用X射线衍射仪表征其晶体结构。实验结果表明:所用溶剂对LVP材料的结构和形貌有显著影响。当选择乙二醇与水混合物(EG∶H_2O=1∶1)作溶剂,在200℃下反应6 h时,可获得粒径小而均匀的LVP微球。