Li4SiO4对CO2捕集性能的实验研究

以Li₂CO₃和SiO₂为原料,通过高温固相合成法合成了CO₂捕集剂Li₄SiO₄,并用X射线粉末衍射仪(XRD)、扫描电子显微镜(SEM)对所合成的材料在CO₂捕集前后的晶相变化以及微观结构进行了表征。通过热重分析仪(TGA)研究了Li₄SiO₄材料吸附CO₂的性能,并在小型热态实验台架上进行了CO₂热态捕集实验。实验结果表明,Li₄SiO₄对CO₂的捕集性能受Li₄SiO₄合成温度、CO₂的吸附温度以及气体中CO₂含量的影响,在700 ℃下制得的Li₄SiO₄具有最佳的CO₂吸附特性,最大吸附增量可达34%。Li₄SiO₄的吸附能力随着CO₂含量和吸附时间的增加而增加,当CO₂浓度分别为75%、67%、60%时,700 ℃ Li₄SiO₄对CO₂最大吸附量分别可达6.68 mmol/g、3.37 mmol/g、2.02 mmol/g (理论量8.33 mmol/g)。     

湿磨法制备纳米Li_4SiO_4材料用于高温捕集CO_2

采用不同硅源、锂源以湿磨法结合高温焙烧制备了纳米Li_4SiO_4材料,利用X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)表征了合成材料的结构和表面形貌,利用热重分析仪(TG)研究了Li_4SiO_4材料高温下的CO_2吸收性能和循环使用稳定性。结果表明,湿磨法制备的Li_4SiO_4材料在550℃、2.5×104Pa下,10min可达吸收平衡,平衡吸收量为27.9%(质量分数),经五次吸收-解吸后仍保持初始吸收性能,显示了良好的循环稳定性。将25%CO_2-25%N2-50%He混合气通过Li_4SiO_4材料床层,发现在550℃下,CO_2能被高效捕集,在相对湿度为10%的水汽存在下,Li_4SiO_4捕集CO_2的性能没有明显下降。     

Kinetic analysis of the thermal stability of lithium silicates (Li4SiO4 and Li2SiO3)

The kinetics describing the thermal decomposition of Li₄SiO₄ and Li₂SiO₃ have been analysed. While Li₄SiO₄ decomposed on Li₂SiO₃ by lithium sublimation, Li₂SiO₃ was highly stable at the temperatures studied. Li₄SiO₄ began to decompose between 900 and 1000 °C. However, at 1100 °C or higher temperatures, Li₄SiO₄ melted, and the kinetic data of its decomposition varied. The activation energy of both processes was estimated according to the Arrhenius kinetic theory. The energy values obtained were −408 and −250 kJ mol⁻¹ for the solid and liquid phases, respectively. At the same time, the Li₄SiO₄ decomposition process was described mathematically as a function of a diffusion-controlled reaction into a spherical system. The activation energy for this process was estimated to be −331 kJ mol⁻¹. On the other hand, Li₂SiO₃ was not decomposed at high temperatures, but it presented a very high preferential orientation after the heat treatments.     

Excess capacity on compound phases of Li2FeTiO4 composite cathode materials synthesized by hydrothermal reaction using optional titanium sources to boost battery performance

Li₂FeTiO₄ composites have been produced using commercial LiAC, FeCl₂ and different titanium sources by hydrothermal synthesis (HS) at 175 ℃ and subsequent annealing at 700 ℃. Impure phase TiO₂, Fe₂O₃ and FeTiO₄ were detected out among the Li₂FeTiO₄ composites with different titanium sources. Micron and nano-sized particles of Li₂FeTiO₄ were prepared from various titanium raw materials, with nano-sized particles predominating when titanium raw materials were layered hydrogen titanate nanowire (H₂Ti₃O₇NW, HTO-NW) and titanium oxide nanotubes (TiO₂NB). The Li₂FeTiO₄ composites synthesized by HTO-NW shows a primary particle size of 50-200 nm of high crystallinity staggered with undissolved nanowire with a diameter size of about 100 nm. The samples using one-dimensional nanometer titanium oxide (TiO₂ NB) as the raw material can get a super high initial discharge capacity of 367.8 mAh/g at the rate of C/10 and excellent cycling stability. The selection of raw materials and adopting multi-phase modification can be considered as an effective strategy to improve the electro-chemical properties of Li₂FeTiO₄ composite cathode materials for the lithium secondary battery.     

Nanosized Spinel Li4Ti5O12 Anode Material Prepared by Gel-polymer Method using Furfuryl Alcohol as Polymerizable Solvent

Nanosized Li₄Ti₅O₁₂ powders are synthesized by a polymerization-based method using ti-tanium butoxide and lithium nitrate as precursors and furfuryl alcohol as a polymerizable solvent. The prepared samples are characterized by X-ray diffraction, scanning electron mi-croscopy, transmission electron microscopy and Braunauer-Emmett-Teller (BET) analysis. The electrochemical performances of these Li₄Ti₅O₁₂ powders are also studied. The effect of different surfactants including citric acid, polyvinylpyrrolidone, and cetyltrimethyl am-monium bromide on the structure and properties is also investigated. It is found that pure spinel phase of Li₄Ti₅O₁₂ is obtained at an annealing temperature of 700 oC or higher. The use of surfactants can improve the powder morphology of nanosized particles with less ag-glomeration. With suitable annealing temperature and the addition of surfactant, Li₄Ti₅O₁₂ powders with high BET surface area and favorable electrochemical performance can be ob-tained.     

Nd3+-doped Li3V2(PO4)3 cathode material with high rate capability for Li-ion batteries

A series of Nd3+-doped Li3NdxV2àx(PO4)3(x = 0.00, 0.02, 0.05, 0.08 or 0.1) composites are synthesized by the rheological phase reaction method. The XRD results indicate that Nd3+ions have been successfully merged into a lattice structure. Doped samples show good electrochemical performance in high discharge rate and long cycle. In the potential range of 3.0–4.3 V, Li3Nd0.08V1.92(PO4)3exhibits an initial discharge capacity of 115.8 m Ah/g at 0.2 C and retain 80.86% of capacity retention at 2 C in the 51 st cycle.In addition, Li3Nd0.05V1.95(PO4)3holds at 100.4 m Ah/g after 80 cycles at 0.2 C with a capacity retention of92.4%. Finally, the CV test proves that the potential polarization of Li3Nd0.08V1.92(PO4)3decreased compared with the un-doped one.     

微波合成法制备锂离子电池正极材料Li2FeSiO4

研究了一种制备锂离子电池正极材料Li2FeSiO4的新方法. 采用机械球磨结合微波热处理合成了Li2FeSiO4正极材料. 通过XRD、SEM和恒流充放电测试, 对样品结构、形貌和电化学性能进行了表征和分析. 与传统固相法合成的材料在晶体结构、微观形貌以及充放电性能方面进行了比较. 结果表明, 微波合成法可以快速制备具有正交结构的Li2FeSiO4材料; 在650 ℃时处理12 min, 获得了纯度高、晶粒细小均匀的产物, 该产物具有较高的放电比容量和良好的循环性能. 在60 ℃下以C/20倍率(电流密度, 1C=160 mA·g-1)进行充放电, 首次放电容量为119.5 mAh·g-1, 10次循环后放电容量为116.2 mAh·g-1. 与传统高温固相法相比, 微波合成法制备的材料具有较高的纯度、均匀的形貌和较好的电化学性能.     

Li3V2(PO4)3电极过程及其锂离子脱嵌动力学研究(I)

采用溶胶凝胶法合成了Nasicon化合物Li₃V₂(PO₄)₃, 采用X射线衍射(XRD)对产品进行了物相分析. 采用充放电测试, 循环伏安(CV)研究了化合物的电化学性能和锂离子的脱嵌过程, 计算出Li^＋在固相中的扩散系数(10^－8 cm²•s^－1); 采用交流阻抗测试(EIS)研究了Li₃V₂(PO₄)₃的电极过程; 对两种类型的阻抗图谱提出不同等效电路模型并对结果进行了拟合; 研究了Li₃V₂(PO₄)₃电极过程动力学以及新鲜电极界面在充放电过程中的变化特性.     

Solid state synthesis of lithiated manganese oxides from mechanically activated Li2CO3–Mn3O4 mixtures

The solid state formation of lithium manganese oxides has been studied from the thermal decomposition of mixtures Li₂CO₃–Mn₃O₄ with X_Li (lithium cationic fraction)=0.33 (LiMn₂O₄), 0.50 (LiMnO₂) and 0.66 (Li₂MnO₃). The analysis of the reactivity has been performed mainly by thermoanalytical (TG/DSC) and diffractometric (XRPD) techniques either on physical mixtures and on mixtures subjected to mechanical activation by high energy milling. At X_Li=0.33, the cubic lithium manganese spinel oxide (LiMn₂O₄) forms in air. TG measurements showed that the reaction starts at a considerably lower temperature in the activated mixture. By variable temperature X-ray diffraction it has been assessed that, upon mechanical activation, LiMn₂O₄ forms directly and its formation is completed within 700 °C whereas, starting from a physical mixture, the formation goes through Mn₂O₃ and is complete only at 800 °C. At T>820 °C LiMn₂O₄ reversibly decomposes to LiMnO₂ and Mn₃O₄ with an enthalpy of 30.05 kJ mol⁻¹ of LiMn₂O₄. At X_Li=0.50, by annealing under nitrogen flow for 6 h at 650 °C the activated mixture, the orthorhombic LiMnO₂ is formed. Such a formation goes through a mixture of LiMnO₂ and LiMn₂O₄. The enthalpy of LiMnO₂ solid state formation from the activated mixture has been determined to be 57.4 kJ mol⁻¹ of LiMnO₂. At X_Li=0.66 in air the mechanical activation considerably lowers the temperature within the monoclinic phase Li₂MnO₃ forms. Besides the reaction enthalpy could be determined as 40.13 kJ mol⁻¹ of Li₂MnO₃. The reaction, when performed under nitrogen flow, goes through the formation of LiMnO₂. Such a first stage of the reaction is affected by the temperature of reaction rather than by mechanical activation. The activation greatly enhances the second stage of the reaction leading from LiMnO₂ to Li₂MnO₃.     

Pt/Cu双金属纳米颗粒的制备及其催化制氢活性

采用化学共还原法合成了聚乙烯吡咯烷酮保护的Pt/Cu双金属纳米颗粒(BNPs),并采用紫外可见吸收光谱、透射电子显微镜、高分辨透射电子显微镜等对所合成的Pt/Cu BNPs进行了表征。研究了化学组成对Pt/Cu BNPs催化Na BH4水解制氢性能的影响。结果表明,所制备的Pt/Cu BNPs平均粒径为1.8~2.3nm,其催化活性远高于单金属Pt和Cu NPs的活性,其中Pt90Cu10BNP的催化活性最高,其在30℃的条件下,催化Na BH4制氢的活性可达6570mol-H2·mol-cat-1·h-1,约为相同粒径的Pt单金属NP的1.6倍。密度泛函理论的计算结果表明,Pt/Cu BNPs优异的催化性能可归因于电荷转移效应,Pt原子与Cu原子之间发生的电子转移使得Pt原子带负电而Cu原子带正电,荷电的Pt和Cu原子成为催化反应的活性中心。     

工艺参数对o-LiMnO2相纯度及Li1.6Mn1.6O4合成的影响及作用（英文）

以MnSO4,KMnO4及LiOH为原料,经水热处理后得到LiMnO2,再由固相焙烧得到尖晶石相Li1.6Mn1.6O4,酸洗处理后得到锂离子筛。研究了水热温度,氧气和MnO4-/Mn2+的物质的量之比(nMnO4∶nMn^2+)对所得LiMnO2的组成及相应前驱体Li1.6Mn1.6O4酸处理中Mn溶损率的影响。开路电势测量及化学分析表明,氧气会参与反应。若按照理论氧化剂用量nMonO4∶nMn^2+=1∶4进行水热反应会导致杂质Li2MnO3和LiMn2O4的生成。若控制水热温度为160℃,nMnO4∶nMn^2+=1∶6时可得到纯相正交LiMnO2(o-LiMnO2)。所得离子筛在高镁锂比盐湖卤水中Li+吸附容量可达42.87 mg·g^-1,且对Li+具有优异的选择吸附性并遵循化学吸附过程。经过5个循环后吸附容量保持在37.21 mg·g^-1,锰溶损率降至0.34%。     

Li4Ti5O12溶胶-凝胶法合成及其机理研究

The precursors of Li₄Ti₅O₁₂ were prepared from tetrabutyl titanate and lithium acetate by sol-gel process. The Li₄Ti₅O₁₂ samples were synthesized by calcining the gel precursors at 400～900 ℃ in air for 6～20 h. Its reaction mechanism was investigated by infrared spectroscopy(IR), thermogravimetry(TG) and X-ray diffraction(XRD). The effects of sinter-temperature, calcination-time and thermal-treatment for the products were discussed. The samples were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM). The results showed that the single-phase products were obtained by calcining the gel precursors at 800 ℃ in air for 20 h, the sinter-temperature was lower than that of solid-state method, the particles were narrowly distributed, well crystallized with a size range from 0.3μm to 0.5 μm.     

Li4Mn5O12包覆对三元正极材料结构和性能的影响

LiNi_1/3Mn_1/3Co_1/3O₂具有很高的理论比容量,但是三元正极材料在高电压下长循环时,其表面结构发生较大的衰退,导致电池的循环性能和倍率性能变差。本文采用耐高电压且结构稳定的富锂尖晶石Li₄Mn₅O₁₂包覆LiNi_1/3Mn_1/3Co_1/3O₂可以有效改善材料的电化学性能。通过XRD、SEM、XPS和TEM等手段对包覆后的材料进行分析,证实了在LiNi_1/3Mn_1/3Co_1/3O₂的表面形成了10nm厚的均匀Li₄Mn₅O₁₂的包覆层;在循环100圈后,包覆后的LiNi_1/3Mn_1/3Co_1/3O₂仍...     

Convenient oxidation of alkylated phenols and methoxytoluenes to antifungal 1,4-benzoquinones with hydrogen peroxide (H2O2)/methyltrioxorhenium (CH3ReO3) catalytic system in neutral ionic liquid

Alkylated phenol and methoxytoluene derivatives were catalytically and selectively oxidized to the corresponding 1,4-benzoquinones in good conversions and yields. Reactions were performed with hydrogen peroxide (H₂O₂)/methyltrioxorhenium (CH₃ReO₃) in 1-butyl-3-methylimidazolium tetrafluoroborate [bmim]BF₄, a neutral ionic liquid. Compounds were tested in vitro for their antifungal activity against the growth of several widespread soil fungi. Some of them were proved to be potent inhibitors of Fusarium sp. than ketoconazole, a commercially available and expensive antifungal agent.     

Cu-Fe-MgO/AlPO_4-5对甲醇水蒸气重整制氢的催化性能研究

以AlPO_4-5分子筛为载体,采用浸渍法制备Cu-Fe-MgO/AlPO_4-5催化剂,用于催化甲醇和水蒸气重整反应制氢气。采用XRD、N2吸附-脱附、H2-TPR、CO2-TPD和NH3-TPD等对催化剂进行表征。结果表明,加入Fe可以明显提高甲醇的转化率,但副产物二甲醚的选择性也增加,添加MgO对降低二甲醚具有明显的作用,但不能提高甲醇的转化率。AlPO_4-5负载Cu、Fe和MgO的质量分数分别为15%、6%和1%时具有较高的催化活性,在反应温度300℃、水醇物质的量比为1.1∶1和质量空速2.51 h~(-1)的条件下,对甲醇的转化率为93.08%,二氧化碳和氢气的选择性分别为95.80%和96.93%,对副产物一氧化碳和二甲醚的选择性分别为1.70%和2.51%。表征结果表明,Cu-Fe-MgO/AlPO_4-5同时含有弱酸弱碱和强酸强碱中心,适量的MgO增加了强碱中心的量,降低弱酸中心的强度,但对强酸中心影响不大。     

Li3V2(PO4)3/C的P123辅助流变相法制备及电化学性能

以V₂O₅、NH₄H₂PO₄、LiOH、柠檬酸、三嵌段聚合物表面活性剂P123为原料, 用流变相(RPR)法制备了Li₃V₂(PO₄)₃/C正极材料. 用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)等方法表征, 结果表明: 材料为单一纯相的单斜晶体结构, 颗粒均匀并呈现珊瑚结构; 恒流充放电, 循环伏安(CV)及电化学交流阻抗(EIS)等电化学性能测试表明, 采用P123 辅助合成材料电化学性能明显优于未采用P123 辅助合成材料. 3.0-4.3 V放电区间, 0.1C充放电下P123 辅助合成Li₃V₂(PO₄)₃/C材料首次放电比容量为129.8 mAh·g^-1, 经过50 次循环后容量只衰减0.9%; 倍率性能及循环性能优异, 1C、10C、25C的首次放电比容量分别为128.2、121.3、109.1 mAh·g^-1, 50次循环后容量保持率分别为99.1%, 96.9%, 90.7%. 这归因于三嵌段聚合物P123 作为分散剂的同时也作为有机碳源在颗粒表面及间隙形成碳网络, 有利于材料导电率的改善, 降低了其电荷转移阻抗, 减小了电极充放电过程的极化现象.     

Effect of surface fluorination and conductive additives on the electrochemical behavior of lithium titanate (Li4/3Ti5/3O4) for lithium ion battery

Effect of surface fluorination and conductive additives on the charge/discharge behavior of lithium titanate (Li_4/3Ti_5/3O₄) has been investigated using F₂ gas and vapor grown carbon fiber (VGCF). Surface fluorination of Li_4/3Ti_5/3O₄ was made using F₂ gas (3 × 10⁴ Pa) at 25-150 °C for 2 min. Charge capacities of Li_4/3Ti_5/3O₄ samples fluorinated at 70 °C and 100 °C were larger than those for original sample at high current densities of 300 and 600 mA/g. Optimum fluorination temperatures of Li_4/3Ti_5/3O₄ were 70 °C and 100 °C. Fibrous VGCF with a large surface area (17.7 m²/g) increased the utilization of available capacity of Li_4/3Ti_5/3O₄ probably because it provided the better electrical contact than acetylene black (AB) between Li_4/3Ti_5/3O₄ particles and nickel current collector.     

Fe3O4(001)-B表面水煤气变换反应机理第一性原理研究

采用自旋极化的密度泛函理论方法系统地研究了Fe_3O_4(001)-B表面水煤气变换的反应机理,计算了整个反应历程。结果表明,对于Fe_3O_4(001)-B表面上的水煤气变换反应,氧化还原、联合和再生三种反应路径共存,但氧化还原和联合机理的有效能垒较低,因而更占优势。对于生成H_2的基元反应,其活性受表面H浓度和催化剂表面O缺陷浓度影响;较高的表面H浓度和O缺陷浓度均有利于H_2生成。这些结果有助于进一步认识铁氧催化剂上的水煤气变换反应机理。     

多元醇法合成具有不同长径比的棒状LiFePO4/C材料

以三价铁盐为铁源,采用多元醇还原法在低温下制备出了具有不同长径比的棒状LiFePO₄材料. 通过X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、循环伏安(CV)、交流阻抗谱(EIS)和恒电流充放电测试等手段分析了不同回流反应时间下制备出的前驱体和最终的LiFePO₄/C 样品. 结果表明：回流反应时间对LiFePO₄的形貌和特性有明显的影响. 通过把回流反应时间从4 h延长至16 h,材料的形貌由不规则的短棒状颗粒变为规则的长棒状颗粒,且棒的直径明显变小. 当回流反应时间为10 h 时,样品复合了多种形貌,有利于电子的传输,在低倍率下具有优秀的性能,0.1C放电比容量为163 mAh·g^-1;当回流反应时间为16 h 时,样品具有最大的长径比,有利于锂离子的扩散,在高倍率下具有良好的性能,1C、3C、5C、10C、20C倍率下放电比容量分别为135、125、118、110、98 mAh·g^-1,循环性能良好,几乎无衰减.     

Structure elucidation of highly polar basic degradants by on-line hydrogen/deuterium exchange hydrophilic interaction chromatography coupled to tandem mass spectrometry

A hydrophilic interaction liquid chromatography (HILIC) method was used to separate a commonly used pharmaceutical starting material, 4-aminomethylpyridine (4-AMP), and its degradants. The structures of the major degradants were characterized and elucidated without prior isolation by accurate mass measurement, MS/MS analysis and on-line hydrogen/deuterium (H/D) exchange experiments. The mass spectra obtained from H/D exchange experiments are particularly useful to differentiate structural isomers, to elucidate the fragmentation pathways, and to aid in structure elucidation in the absence of MS/MS fragmentation information. The impact of deuterium oxide and temperature on HILIC separation has also been explored here. The integration of H/D exchange with HILIC has been described here for the first time and has been demonstrated to be a powerful structure elucidation tool via the study of degradants in 4-AMP.