助熔剂LiBO2对Li1.3Al0.3Ti1.7(PO4)3性质的影响

采用溶胶-凝胶法合成了Li1.3Al0.3.Ti1.7(PO4)3粉末,然后添加不同摩尔分数的LiBO2助熔剂在900℃烧结2h制备了Li1.3Al0.3.Ti1.7(PO4)3烧结片样品.通过X射线衍射和扫描电子显微镜分析了合成产物的相组成与形貌,采用循环伏安及交流阻抗技术研究了产物的氧化-还原电位、离子电导率与活化...     

不同热处理方式对Li1.3Al0.3Ti1.7(PO4)3薄膜性质的影响研究

采用快速退火和常规退火两种不同热处理方式制备Li1.3Al0.3Ti1.7(PO4)3薄膜,用X射线衍射、扫描电子显微镜、循环伏安及交流阻抗等技术分析检测薄膜物相、形貌、电化学窗口、离子电导率及电导活化能。结果表明,两种退火方式制备的薄膜均为纯相Li1.3Al0.3Ti1.7(PO4)3,制备的薄膜均匀、无龟裂,但采用快速退火制备的薄膜晶粒比采用常规退火制备的薄膜要小,薄膜更光滑更致密。两种退火方式制备的薄膜电化学窗口都超过了2.4 V,薄膜离子电导率分别为2.7×10-6 S/cm和1.4×10-6 S/cm。采用快速退火制备的Li1.3 Al0.3 Ti1.7(PO4)3薄膜离子电导活化能比采用常规退火制备的薄膜要小。     

凝胶注模工艺制备三维多孔Li1.3Al0.3Ti1.7(PO4)3固态电解质

三维多孔固态电解质是连续型复合电解质的骨架部分。采用共沉淀法制备Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3固态电解质粉体,再通过凝胶注模工艺合成了Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3多孔坯体,并在不同温度下烧结,比较了烧结体的物相组成、显微形貌、收缩率、孔隙率、电导率和激活能。结果表明:在900℃以上烧结,坯体发生明显的致密化,并且产生更多的杂相,其致密度升高而电导率降低。在800℃烧结的样品,孔隙率在50%以上,具有6.94×10–5 S/cm的电导率,激活能为0.27 eV。所得多孔坯具有较高的孔隙率和电导率,使其适合作为三维有机–无机复合固态电解质的陶瓷框架。     

Li4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3复合负极材料的制备及其性能*

采用溶胶-凝胶法合成Li4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3复合负极材料,通过X射线衍射、扫描电子显微镜、恒电流充放电、循环伏安和电化学阻抗研究复合材料的结构、形貌及电化学性能。结果表明：溶胶-凝胶法能合成纯相Li4Ti5O12/Li1.3Al0.3Ti1.7(PO4)3复合负极材料,所合成材料颗粒均匀。与纯相Li4Ti5O12相比,引入Li1.3Al0.3Ti1.7(PO4)3的Li4Ti5O12复合负极材料具有更低的锂离子嵌入/脱出阻抗,Li1.3Al0.3Ti1.7(PO4)3质量分数为1%、2%、3%、4%、5%的Li4Ti5O12复合材料首次放电容量比纯相Li4Ti5O12分别提高了6.2%、11.8%、15.5%、8.0%和2.0%。Li1.3Al0.3Ti1.7(PO4)3质量分数为3%的Li4Ti5O12复合负极材料20次循环后每次循环容量衰减率为0.022%,循环性能最好。     

(NH4)2SO4作助熔剂对单氟磷酸钠合成的影响

以六偏磷酸钠和氟化钠为合成单氟磷酸钠的主要反应原料,根据助熔剂的性质,筛选出(NH4)2SO4为较佳助熔荆.采用单因素实验法考察了干燥温度、干燥时间、合成温度、合成时间、氟磷比、n[(NH4)2SO4]:n(NaPO3)6+NaF]对反应的影响.通过正交实验优选,确定了最佳工艺条件.     

固体电解质Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3烧结片的制备与表征

以固相法合成固体电解质Li1.3Al0.3Ti1.7(PO4)3(LATP)粉末。研究了烧结温度以及烧结时间对LATP离子电导率的影响。采用X射线衍射、扫描电子显微镜和交流阻抗技术对材料粉末以及烧结片相组成、结构和离子导电性进行表征。结果表明,900℃条件下合成的粉末为纯相LATP,颗粒均匀,当LATP电解质基片在900℃下烧结4 h,得到的LATP烧结片表面致密光滑,而且离子电导率较高,为3.03×10-4S/cm。     

助熔剂对宁东煤灰熔融特性影响的研究

通过添加CaCO3、MgO和Fe2O3三种助熔剂,考察其对宁东矿区两种煤样（1#、2#）灰熔融温度的影响,并利用三元相图及XRD对煤灰矿物组成进行分析.结果表明：在高温下煤灰中矿物质之间形成低温共熔物,使煤灰的灰熔点降低,且硅铝比较低的煤样具有较低的灰熔融温度.实验表明在弱还原性气氛中,三种助熔剂对2#煤样灰熔融温度的降低效果较明显.     

氯化物助熔剂对Y3Al5O12:Ce3+荧光粉性能的影响

选用卤化物LiCl、NaCl、KCl和SrCl2等作为助熔剂,合成了一系列YAG∶Ce粉体,并研究了助熔剂对YAG∶Ce荧光粉晶相、形貌和发光性能的影响.结果表明适量助熔剂有利于YAG∶Ce荧光粉的晶化,合成的荧光粉具有石榴石的结构,规则的形貌和窄的粒度分布.添加适量助熔剂可以提高YAG∶Ce荧光粉的发光强度.最适宜的添加量分别是:LiCl 10%,NaCl 7%,KCl 7%,SrCl,4%.     

助熔剂对Y_2O_2S∶Ti长余辉磷光体发光性能的影响(英文)

用高温固相还原法合成了无稀土激活离子Y2O2S∶0.09Ti长余辉发光材料,研究了 Li2CO3,Na2CO3,K2CO3,K3PO4和K2HPO4等 5种助熔剂对Y2O2S∶Ti磷光体发光性能的影响。结果表明:除了 K2HPO4外,加入 Li2CO3,Na2CO3, K2CO3与 K3PO4助熔剂均可得到单相Y2O2S∶Ti晶体。发射光谱结果显示:不同助熔剂的加入并没有改变样品发射谱主峰位置(565 nm),但对其峰强度产生明显影响。助熔剂也显著改善了Y2O2S∶Ti的余辉亮度,特别是Li2CO3。10 min衰减时,Y2O2S∶Ti样品的余辉亮度从加 K2CO3助熔剂的0.15 mcd/m2增加到加Li2CO3助熔剂的10.1 mcd/m2。用紫外光激发样品,移去光源后,加Li2CO3助熔剂合成的样品在暗室中的余辉时间可持续达 5 h(0.32 mcd/m2) 。     

助熔剂种类对硅藻土助滤剂过滤性能的影响研究

以临江硅藻土提纯精土为原料,进行添加不同阳离子种类助熔剂、不同阴离子种类助熔剂及多种复合助熔剂焙烧制备硅藻土助滤剂对比试验,结果表明,助熔剂NaNO3效果最佳,添加量为硅藻土质量的11％时,渗透率可达13.58 darcy,啤酒吸光度从1.900降至0.160;NaNO3与KCl组合的复合助熔剂效果最优,质量比为1∶1,添加量为硅藻土质量的10％时,助滤剂渗透率达到9.78 darcy,啤酒吸光度从1.900降至0.135.     

固体电解质包覆LiMn2O4正极材料的合成及表征

采用湿化学法制备Li1.3Al0.3Ti1.7(PO4)3包覆LiMn2O4。采用X射线衍射、扫描电镜、恒电流充放电等技术对合成产物进行物相、形貌和电化学分析。结果表明:Li1.3Al0.3Ti1.7(PO4)3包覆LiMn2O4与LiMn2O4有相似的X射线衍射结果,且包覆后的LiMn2O4循环伏安峰电流和电荷转移阻抗变化不大。室温及55℃,以0.2 C充放电倍率循环40次时,Li1.3Al0.3Ti1.7(PO4)3包覆LiMn2O4的容量保持率分别为98.2%和93.7%,未包覆的LiMn2O4的容量保持率分别为85.4%和79.1%。当以2 C倍率室温充放电循环时,Li1.3Al0.3Ti1.7(PO4)3包覆LiMn2O4的容量保持率比未包覆的LiMn2O4高8%;55℃充放电循环时,Li1.3Al0.3Ti1.7(PO4)3包覆LiMn2O4的容量保持率比未包覆的LiMn2O4高11.1%。     

Li1.3Al0.3Ti1.7(PO4)3 ceramic electrolyte fabricated from bimodal powder precursor

A novel approach is proposed to design high-quality NASICON–type solid-state electrolytes (SSEs) based on Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) by incorporating nanoparticles into a matrix of microparticles, which could efficiently improve densification of LATP SSEs by sintering. Moreover, LATP SSEs with bimodal microstructures are obtained by tuning mass ratio of 60 nm and 600 nm ceramic particles, which are fabricated by sol-polymer and molten quenching methods, respectively. The LATP SSE containing 60 nm and 600 nm particles with the mass ratio of 10%/90% displays a high ionic conductivity of (5.93 ± 0.24)× 10⁻⁴ S/cm at room temperature and relative density of 95.5 ± 1.1% after sintering at 900 °C for 6 h. Besides, the Li||LATP||Li symmetric cell with the mass ratio of 10%/90% exhibits better cyclic stability with a steady polarization voltage of 121.2 mV than that of other ratios. Therefore, SSEs with multimodal microstructures pave a promising venue for practical application of high-energy-density and safe solid-state Li metal battery.     

Enhancing purity and ionic conductivity of NASICON-typed Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte

Increasing demand for safe energy storage and portable power sources has led to intensive investigation for all-solid state Li-ion batteries and particularly to solid electrolytes for such rechargeable batteries. One of the most promising types of solid electrolytes is NASICON-structured Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) due to its relatively high ionic conductivity and stability towards air and moisture. Here, the work is aimed on implementing the steps to hinder formation of impurity phases reported for various synthesis routes. Consequently, the applied modifications in the preparation strategies alter a crystal shape and size of prepared material. These two parameters have an enormous impact on properties of LATP. Fabrication of larger particles with a cubic shape significantly improves its ionic conductivity. As a result, LATP preparation methods such as a solution chemistry and molten flux resulted in the highest ionic conductivity samples with the value of ~10^?4 S cm^?1 at room temperature. Other LATPs obtained by solid-state reaction, sol-gel and spray drying methods depicted the ionic conductivity of ~10^?5 S cm^?1. The activation energy of lithium ion transfer in LATP varied in a range of 0.25–0.4 eV, which is in well agreement with the previously reported data.     

Effect of SnO–P2O5–MgO glass addition on the ionic conductivity of Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte

NASICON-type structured compounds Li_1+xM_xTi_2-x(PO₄)₃ (M = Al, Fe, Y, etc.) have captured much attention due to their air stability, wide electrochemical window and high lithium ion conductivity. Especially, Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) is a potential solid electrolyte due to its high ionic conductivity. However, its actual density usually has a certain gap with the theoretical density, leading the poor ionic conductivity of LATP. Herein, LATP solid electrolyte with series of SnO–P₂O₅–MgO (SPM, 0.4 wt%, 0.7 wt%, 1.0 wt%, 1.3 wt%) glass addition was successfully synthesized to improve the density and ionic conductivity. The SPM addition change Al/Ti–O bond and P–O bond distances, leading to gradual shrinkage of octahedral AlO₆ and tetrahedral PO₄. The bulk conductivity of the samples increases gradually with SPM glass addition from 0.4 wt% to 1.3 wt%. Both SPM and the second-phase LiTiPO₅, caused by glass addition, are conducive to the improvement of compactness. The relative density of LATP samples increases first from 0 wt% to 0.7 wt%, and then decreases from 0.7 wt% to 1.3 wt% with SPM glass addition. The grain boundary conductivity also changes accordingly. Especially, the highest ionic conductivity of 2.45 × 10^?4 S cm^?1, and a relative density of 96.72% with a low activation energy of 0.34 eV is obtained in LATP with 0.7 wt% SPM. Increasing the density of LATP solid electrolyte is crucial to improve the ionic conductivity of electrolytes and SPM glass addition can promote the development of dense oxide ceramic electrolytes.     

Structural and electrical properties of ceramic Li-ion conductors based on Li1.3Al0.3Ti1.7(PO4)3-LiF

The work presents the investigations of Li_1.3Al_0.3Ti_1.7(PO₄)₃-xLiF Li-ion conducting ceramics with 0 ≤ x ≤ 0.3 by means of X-ray diffractometry (XRD), ⁷Li, ¹⁹F, ²⁷Al and ³¹P Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) spectroscopy, thermogravimetry (TG), scanning electron microscopy (SEM), impedance spectroscopy (IS) and density method. It has been shown that the total ionic conductivity of both as-prepared and ceramic Li_1.3Al_0.3Ti_1.7(PO₄)₃ is low due to a grain boundary phase exhibiting high electrical resistance. This phase consists mainly of berlinite crystalline phase as well as some amorphous phase containing Al³⁺ ions. The electrically resistant phases of the grain boundary decompose during sintering with LiF additive. The processes leading to microstructure changes and their effect on the ionic properties of the materials are discussed in the frame of the brick layer model (BLM). The highest total ionic conductivity at room temperature was measured for LATP-0.1LiF ceramic sintered at 800 °C and was equal to σ_tot = 1.1 × 10⁻⁴ S cm⁻¹.     

Characterization of (PEO)LiClO4‐Li1.3Al0.3Ti1.7(PO4)3 composite polymer electrolytes with different molecular weights of PEO

A group of polyethylene oxide (PEO)LiClO₄‐Li_1.3Al_0.3Ti_1.7(PO₄)₃ composite polymer electrolyte (CPE) films was prepared by the solution‐cast method. In each film, EO/Li = 8 and the Li_1.3Al_0.3Ti_1.7(PO₄)₃ content of 15 wt % were fixed, but the number averaged molecular weight of PEO (M_n) was altered from 5 to 7 × 10⁴ to 10⁶, 2.2–2.7 × 10⁶, 3–4 × 10⁶, 4–5 × 10⁶, and 5.5–6 × 10⁶, respectively. Several techniques including X‐ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and electrical impedance spectroscopy (EIS) were used to characterize the CPE films. LiClO₄ was found to have a strong tendency to complex with PEO, but Li_1.3Al_0.3Ti_1.7(PO₄)₃ was rather dispersed in PEO matrix. DSC analysis revealed that the amorphous phase was dominant in the CPE films although the PEOs before‐use was considerably crystalline. SEM study showed smooth and homogeneous morphologies of the films with low molecular weight PEO and a dual phase characteristic for those with high molecular weight PEO. EIS results indicated that the CPE films are all ionic conductor and the conducting behavior obeys Vogel‐Tamman‐Fulcher (VTF) equation. The parameters in VTF equation were obtained and discussed by taking into considerations PEO molecular weights and crystallinities of the CPE films. Of all the films, the one with PEO with the smallest M_n = 5–7 × 10⁴ had the maximum conductivity, i.e., 1.590 × 10^?5 S cm^?1 at room temperature and 1.886 × 10^?3 S cm^?1 at 373 K. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4269–4275, 2006     

Lithium conducting solid electrolyte Li1.3Al0.3Ti1.7(PO4)3 obtained via solution chemistry

NaSICON-type lithium conductor Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) is synthesized with controlled grain size and composition using solution chemistry. After thermal treatment at 850 °C, sub-micronic crystallized powders with high purity are obtained. They are converted into ceramic through Spark Plasma Sintering at 850–1000 °C. By varying the processing parameters, pellet with conductivities up to 1.6 × 10^?4 S/cm with density of 97% of the theoretical density have been obtained. XRD, FEG-SEM, ac-impedance and Vickers indentation were used to characterize the products. The influence of sintering parameters on pellet composition, microstructure and conductivity is discussed in addition to the analysis of the mechanical behavior of the grains interfaces.     

溶胶-凝胶法制备NASICON型Li_(1.15)Y_(0.15)Zr_(1.85)(PO_4)_3固态电解质

以碳酸锂、硝酸锆、磷酸氢二铵和硝酸钇为原料,柠檬酸为络合剂,采用溶胶–凝胶法制备了NASICON型Li1.15Y0.15Zr1.85(PO4)3固态电解质材料,通过无压烧结和放电等离子烧结(SPS)得到固态电解质片。结果表明:采用无压烧结在1 150℃制备的电解质密度可以达到理论密度的95.2%,在室温下晶粒电导率和总电导率分别为2.19×10–4 S/cm和0.86×10–4 S/cm;采用SPS在1 150℃烧结得到的电解质片密度可达到理论密度的96.8%,在室温下样品总电导为0.97×10–4S/cm,激活能为0.44 e V。四方相Zr O2的存在是样品激活能升高的主要原因。     

Kinetic Analysis of Crystallization in Li1.3Al0.3Ti1.7(PO4)3 Glass Ceramics

The crystallization mechanisms for Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) glass ceramics were studied using thermophysical property characterization techniques. Differential scanning calorimetry (DSC) revealed two separate exothermic events that were ascribed to the initial growth and growth to coherency of a dendritic phase. It was found that the commonly used Johnson‐Mehl‐Avrami is not a suitable kinetic model for this material. Rather, the Sestak‐Berggren (SB) autocatalytic kinetic model was used to analyze the DSC data and the activation energy for initial growth (259 kJ/mol) and coherency (272 kJ/mol) was calculated using isoconversional methods. The calculated parameters for the SB model were used to compare experimental and calculated values for heat flow during the crystallization of LATP and good fits were found for both exothermic events.