COMPUTERIZED SIMULATION OF MOLTEN SALT SOLUTION OF Li,KF,Cl SYSTEM BY MOLECULAR DYNAMIC METHOD

The structure and properties of molten salt solution o J Li,K|F,Cl system have been investiged by computerized simulation of molecular dynamic method.The partial RDF,the partial molar energy of mixing and the diffusion coeffients of Li^+,K^+,F^- and Cl^- have been calculated. The results are in agreement with the experimental values.The regularities of the distribution of ions and mieroscopic holes are discussed based on the results of computerized simulation.

Electrochemical performances of LiFePO_4/C composites prepared by molten salt method

LiFePO4/C composites were synthesized by a molten salt (MS) method using the mixture of LiCl,LiOH and NaCl.The prepared LiFePO4/C composites are characterized by X-ray diffractometry (XRD),field emission scanning electron microscopy (FESEM) and charge-discharge test.XRD patterns indicate that LiFePO4 prepared in the temperature range of 550-700 ℃ crystallizes well in an olivine-type structure.Through FESEM images,the sphere-like and homogeneous particles of 0.2 μm can be observed.The charge-discharge test shows that the materials prepared at 600 ℃ for 12 h have good electrochemical performance.At the rates of 0.2C (34 mA/g) and 0.5C,the discharge capacities are 144.6 and 122.3 mA·h/g,respectively,together with good cycle performances.

Structural and Piezoelectric Properties of Sr_(0.6)Ba_(0.4)Nb_2O_6 Micro-rods Synthesized by Molten-Salt Method

Sr0.6 Ba0.4 Nb2 O6 micro-rods are prepared by the molten-salt method with K2 SO4,KCl-K2 SO4,and KCl as fluxes.It reveals that the Sr0.6 Ba0.4 Nb2 O6 synthesized with KCl as a flux exhibits a single phase with tetragonal tungsten bronze structure.The measurement of X-ray diffraction indicates that the Sr0.6 Ba0.4 Nb2 O6 micro-rods synthesized at 1 300℃are anisotropic.The morphology of the powers is examined by transmission electron microscope.It reveals that the length-diameter ratio of Sr0.6 Ba0.4 Nb2 O6 micro-rods increases with increasing annealing temperature from 900℃to 1 300℃.At 1 300℃,the rod possesses a large length-diameter ratio of 8∶1.Moreover,the analysis of the piezoelectric properties of single micro-rods using apiezo-response force microscope indicates that the domains of the material are arranged along its radial direction.

Preparation of titanium dioxide from titania-rich slag by molten NaOH method

Preparing titanium dioxide from titania-rich slag （TiO2 73wt%） by molten NaOH method has been developed. The effects of temperature and reaction time on the titanium conversion were investigated. The results showed that temperature had significant influence on the titanium conversion as well as the structure of the product. About 92% of titanium in the titania-rich slag could be converted after reacting with NaOH at 500℃ for 1 h. Metatitanic acid was formed through the steps of washing treatment, acid dissolution, and hydrolysis. Well-dispersed spherical titanium dioxide particles with an average size of 0.1-0.4μm can be obtained by calcination of metatitanic acid. In addition, the content of titanium dioxide in the product is up to 98.6wt%, which can be used as pigments after further treatment of coating and crushing.

Flow field effect of delayed neutron precursors in liquid-fueled molten salt reactors

In molten salt reactors(MSRs),the liquid fuel salt circulates through the primary loop and a part of the delayed neutron precursors(DNPs)decays outside the reactor core.To model and analyze the flow field effect of DNPs in channel-type liquid-fueled MSRs,a three-dimensional space-time dynamics code,named ThorCORE3D,that couples neutronics,core thermalhydraulics,and a molten salt loop system was developed and validated with the Molten Salt Reactor Experiment(MSRE)benchmarks.The effects of external loop recirculation time,fuel flow rate,and core flow field distribution on the delayed neutron fraction loss of MSRE at steadystate were modeled and simulated using the ThorCORE3D code.Then,the flow field effect of the DNPs on the system responses of the MSRE in the reactivity insertion transient under different initial conditions was analyzed systematically for the channel-type liquid-fueled MSRs.The results indicate that the flow field condition has a significant effect on the steady-state delayed neutron fractions and will further affect the transient power and temperature responses of the reactor system.The analysis results for the effect of the DNP flow field can provide important references for the design optimization and safety analysis of liquid-fueled MSRs.

The protective performance of a molten salt frozen wall in the process of fluoride volatility of uranium

The fluoride volatility method (FVM) is a technique tailored to separate uranium from fuel salt of molten salt reactors. A key challenge in R&D of the FVM is corrosion due to the presence of molten salt and corrosive gases at high temperature. In this work, a frozen-wall technique was proposed to produce a physical barrier between construction materials and corrosive reactants. The protective performance of the frozen wall against molten salt was assessed using FLiNaK molten salt with introduced fluorine gas, which was regarded as a simulation of the FVM process. SS304, SS316L, Inconel 600 and graphite were chosen as the test samples. The extent of corrosion was characterized by an analysis of weight loss and scanning electron microscope studies. All four test samples suffered severe corrosion in the molten salt phase with the corrosion resistance as: Inconel 600>SS316L>graphite>SS304. The presence of the frozen wall could protect materials against corrosion by molten salt and corrosive gases, and compared with materials exposed to molten salt, the corrosion rates of materials protected by the frozen wall were decreased by at least one order of magnitude.

COMPUTERIZED SIMULATION OF THERMODYNAMICS FOR MOLTEN LiF-KF SOLUTION BY MONTE CARLO METHOD

The structure and behaviour of LiF-KF solution,as a typical common-anion system,has been simulated by Monte Carlo method.The calculation of partial radial distribution function of ions,heat of mixing and potential energy distribution shows that the average distance be- tween Li^+ and F^- ions will significantly narrow after mixing of molten LiF and KF.This is very similar to the lean-on-one-side effect in molten LiF-KCl solution.The calculated heat of mixing is in fair agreement with the measured one.The dominant source of the energy of mixing may be that the decrease of the repulsion energy between cations,the decrease of the attraction energy between cations and anions,and the decrease of the repulsion energy be- tween anions.

COMPUTER SIMULATION OF STRUCTURE OF MOLTEN DyF_3－BaF_2－LiF SYSTEM BY MONTE CARLO METHOD

ＣＯＭＰＵＴＥＲＳＩＭＵＬＡＴＩＯＮＯＦＳＴＲＵＣＴＵＲＥＯＦＭＯＬＴＥＮＤｙＦ_３－ＢａＦ_２－ＬｉＦＳＹＳＴＥＭＢＹＭＯＮＴＥＣＡＲＬＯＭＥＴＨＯＤ￥ＸｕＣｈｉ；ＳｕＨａｎｇ；ＣｈｅｎＮｉａｎｙｉ（ＳｈａｎｇｈａｉＩｎｓｔｉｔｕｔｅｏｆＭｅｔａｌｌ...

Etching Mechanism of Ti_(3)C_(2)Cl_(2) MXene Phases by CuCl_(2)-Lewis Molten Salt Method

We described a method for obtaining fluorine-free Ti_(3)C_(2)Cl_(2)MXene phases by melting copper in CuCl_(2)instead of aluminum in Ti_(3)AlC_(2).XRD results show that when molten salt CuCl_(2)etches Ti_(3)AlC_(2),it forms an intermediate product Ti_(3)CuC_(2),and then reacts with Ti_(3)CuC_(2)to obtain Ti_(3)C_(2)Cl_(2).The reaction of Ti_(3)AlC_(2)and CuCl_(2)at a temperature of 800℃for 2 h to obtain Ti_(3)C_(2)Cl_(2)with an optimal lamellar structure is shown in SEM results.The pseudopotential plane-wave(PP-PW)method is used to calculate on the electronic structure.The etching mechanism is investigated by the total energies of each substance.The chemical reaction of Ti_(3)AlC_(2)and CuCl_(2)will first become Ti_(3)CuC_(2)and Cu,and then become Ti_(3)C_(2)Cl_(2)during the Lewis acid etching process,which are consistent with the experimental results.

NdF_(3)在LiF熔盐中的溶解及离子结构

LiF-NdF_(3)熔盐体系中离子的构成形式对解析电解钕工艺的电解过程至关重要,本文采用冰点降低法分析LiF-NdF_(3)熔盐体系的离子结构。通过Temkin和Flood模型及热力学计算分析熔盐体系内可能存在的离子团簇,结果表明,NdF_(3)在LiF中的溶解模型符合TemkinⅠ、TemkinⅡ、TemkinⅥ、TemkinⅦ和FloodⅡ、FloodⅥ、FloodⅦ,在LiF-NdF_(3)熔盐体系中主要形成含有1~2个Nd^(3+)的分子团簇,NdF_(3)在LiF内溶解主要形成游离的Nd^(3+)、F-、Li^(+)以及Li^(+)·[NdF_(4)]^(-)、Li^(+)·[Nd2F7]-、2Li^(+)·[Nd_(2)F_(8)]^(2-)分子团簇。

熔盐辅助合成硼化铪工艺研究

这是一篇冶金工程领域的论文。以氧化铪和碳化硼为原料,采用氯化钠为熔盐介质,通过硼/碳热还原法合成了纯度较高的硼化铪粉体。研究了反应温度、保温时间等合成工艺参数以及原料配比对材料晶相组成和显微结构的影响。结果表明,以氯化钠为熔盐介质时,氧化铪在1300℃的合成温度下开始转化为硼化铪,其温度远低于传统的硼化铪合成所需温度。在硼过量20%,反应温度和保温时间分别为1400℃和2 h所制备的硼化铪粉体纯度较高,X射线衍射中可以明显观察到硼化铪结晶峰,且在扫描电镜中可以观察到紧密团聚形貌的硼化铪。

(Si_(0.2)Ti_(0.2)Nb_(0.2)Ta_(0.2)V_(0.2))C高熵陶瓷的低温制备及吸波性能

寻求具有良好耐高温及力学性能的新型陶瓷材料是吸波材料领域的研究热点之一。高熵碳化物陶瓷具有高温热稳定性及抗氧化性好等优点,但合成温度高且吸波性能研究较少,限制了其在高温吸波材料领域的应用。本工作采用熔盐法合成了多晶岩盐晶型(Si_(0.2)Ti_(0.2)Nb_(0.2)Ta_(0.2)V_(0.2))C高熵碳化物陶瓷,研究了其物相组成、微观形貌及吸波特性。结果表明:随着反应温度的升高,样品的衍射峰逐渐锐化,吸波性能明显提高。当反应温度为1500℃时,3.72 GHz时最低反射损耗达-34.68 dB;与已报道的高熵碳化物陶瓷相比,在相同的有效吸收带宽(2.3 GHz)下,涂层厚度减少了13.3%(1.5 mm降低到1.3 mm),其介电损耗主要来源于极化损耗和导电损耗。本工作制备的高熵碳化物陶瓷可以为研究制备新型环境适应、耐高温、抗冲击的高性能单相吸波材料提供新途径。

LiF-[CaF_(2)/YbF_(3)]-Yb_(2)O_(3)熔盐及Yb-Ni合金密度特性研究

LiF-[CaF_(2)/YbF_(3)]-Yb_(2)O_(3)熔盐体系的密度是电解法制备稀土Yb合金的重要参数。本文采用阿基米德法测量和分析在1173~1573 K温度范围内LiF-[CaF_(2)/YbF_(3)]-Yb_(2)O_(3)体系的密度及其变化规律,同时,利用数学模型估测Yb-Ni合金密度,分析电解过程中熔盐与合金的分离性,结果表明:在1173~1573 K温度范围内,(LiF-CaF_(2))eut(eut为熔盐体系共晶点)体系与(LiF-YbF_(3))eut体系密度均随温度升高而线性降低,同时,摩尔体积均随温度线性递增;(LiF-YbF_(3))eut体系过剩体积随温度线性递减;在1173~1573 K温度区间和Yb_(2)O_(3)质量分数在0~4%范围内,当Yb_(2)O_(3)含量一定时,(LiF-CaF_(2))eut-Yb_(2)O_(3)和(LiF-YbF_(3))eut-Yb_(2)O_(3)熔盐体系的密度均随温度升高而线性降低,当温度一定时,(LiF-CaF_(2))eut-Yb_(2)O_(3)体系在0≤x(Yb_(2)O_(3))≤2.5%范围内呈线性递增,而((LiF-YbF_(3))eut-Yb_(2)O_(3)体系在0≤x(Yb_(2)O_(3))≤3.5%范围内呈线性递增;Yb-Ni合金的密度要高于LiF-[CaF_(2)/YbF_(3)]-Yb_(2)O_(3)熔盐体系的密度,在电解过程中易于分离。

Ba_(3)(VO_(4))_(2):Sm^(3+)荧光粉的熔盐法合成及其温度传感特性

采用熔盐法成功合成了Ba_(3-x)(VO_(4))_(2):xSm^(3+)(x=0.02~0.16)一系列荧光粉,探讨了合成条件、Sm^(3+)掺杂对样品结构和发光性能的影响,并探究了样品的温度传感性能。结果表明:合成样品的适宜反应条件是煅烧温度为900℃、煅烧时间为1 h、原料与熔盐质量比为1∶3,所得样品相纯度和结晶度均较高。样品微观形貌呈片状,厚度约1.5~3 mm。在318 nm激发下,Ba_(3-x)(VO_(4))_(2):xSm^(3+)的发射光谱中可同时观察到VO_(4)^(3-)基团的宽带发射和Sm^(3+)的特征发射,样品的发光颜色集中在黄白光区域。随着Sm^(3+)掺杂浓度(x)从0.02增大到0.16,Sm^(3+)的特征发射峰强度呈现出先升后降的变化趋势,当x=0.10时,发射峰强度达到最高值。导致其浓度猝灭的主要原因是电偶极-电偶极(d-d)相互作用。在298~473 K的温度范围内,Ba_(2.9)(VO_(4))_(2):0.10Sm^(3+)荧光粉中Sm^(3+)(652 nm)和VO_(4)^(3-)基团(504 nm)发射的荧光强度比呈现明显的温度依赖性,其最大绝对灵敏度为0.36 K^(-1),最大相对灵敏度为1.99%K^(-1)。因此,Sm^(3+)掺杂Ba_(3)(VO_(4))_(2)的荧光粉具有优异的温度传感性能,在非接触式光学测温中具有潜在的应用价值。

铝-空气电池废电解液制备片状氧化铝的研究

以铝-空气电池废电解液为原材料,用硫酸铝调节pH值,用硫酸钾作为熔盐制备片状氧化铝(α-Al_(2)O_(3)),研究了合成温度、晶种添加量对α-Al_(2)O_(3)粉体体积分数、粒度大小及粒度分布的影响规律。通过X射线衍射仪、扫描电子显微镜和激光粒度仪等,对加入不同晶种量的α-Al_(2)O_(3)粉体的结构和形貌进行表征。结果表明,添加晶种后可以提高α-Al_(2)O_(3)粉体的体积分数,减小α-Al_(2)O_(3)粉体的粒度,使α-Al_(2)O_(3)粉体的粒度分布更集中,同时使α-Al_(2)O_(3)粉体更分散。此外,当晶种添加量为5%(质量分数)时,制备出的片状α-Al_(2)O_(3)的体积分数可达97.0%,平均粒度约为7.24μm。

熔盐法制备Co_(9)S_(8)/C锂离子电池负极材料及其性能研究

以氯化钴为钴源,硫脲为硫源,柠檬酸为碳源,冷冻干燥后,采用熔盐法在不同的温度进行退火处理得到Co_(9)S_(8)与C的复合物CS(CS-600,CS-700,CS-800,CS-900)。系统地探讨了不同的退火温度对产物的晶体结构、形貌及电化学性能的影响。结果发现:和纯Co_(9)S_(8)样品相比,碳复合的Co_(9)S_(8)样品的循环性能与倍率性能得到了较大的提升。在煅烧温度为700℃时,所合成的样品CS-700具有最高的比容量与最好的循环性能,在100 mA·g^(-1)充放电循环100次后,放电比容量可以达到898.6 mAh·g^(-1),可作为锂离子电池负极材料的潜在选择。

NaCa_(2)Mg_(2)(VO_(4))_(3)∶Eu^(3+)颜色可调荧光粉的熔盐法合成及其发光性能研究

以廉价的NaCl为熔盐,采用熔盐法合成了NaCa_(2-x)Mg_(2)(VO_(4))_(3)∶xEu^(3+)(0≤x≤0.10)系列颜色可调荧光粉,系统研究了合成条件、Eu^(3+)掺杂对样品结构及发光性能的影响。结果表明,反应温度为800℃、反应时间为0.5 h、原料与熔盐的质量比为1∶3是合成NaCa_(2)Mg_(2)(VO4)_(3)的适宜反应条件,所得样品为NaCa_(2)Mg_(2)(VO_(4))_(3)纯相,且结晶度高。样品微观形貌随着反应温度的升高由珊瑚状演变为表面光滑的不规则多面体。Eu^(3+)掺杂对NaCa_(2)Mg_(2)(VO_(4))_(3)的晶体结构影响较小,但对其发光性能影响较大。随着Eu^(3+)浓度(x)的增加,VO_(4)^(3-)的特征发射带强度逐渐减弱;而Eu^(3+)的特征发射峰强度先增大后减小,当x=0.06时,达到最大。故通过改变Eu^(3+)浓度,可对样品的发光颜色进行调制,从绿色可调制为黄绿色、黄色、黄白色、橙红色。荧光光谱与荧光寿命分析表明,NaCa_(2)Mg_(2)(VO_(4))_(3)∶Eu^(3+)体系中存在VO43-到Eu^(3+)的能量转移过程,能量转移效率约为23%;热稳定性分析结果表明,当温度从室温(298.15 K)升高到398.15 K时,NaCa_(1.94)Mg_(2)(VO_(4))_(3)∶0.06Eu^(3+)荧光粉在614 nm处的主发射峰强度可保留起始值的68.4%,表现出良好的热稳定性。

水溶液法制备的前驱体对g-C_(3)N_(4)结构及其催化活性的影响

通过以水溶液法制备的氯化钠改性三聚氰胺为前驱体,制备了石墨相氮化碳。研究不同氯化钠加入量对熔融盐法制备的石墨相氮化碳材料结构和性能的影响。通过以亚甲基蓝(MB)为目标污染物的光催化模拟实验,表明当氯化钠添加量为1 g时,煅烧产物GCN-1的光催化性能最佳,其一级降解速率常数为0.01112 min^(-1),约为原始氮化碳的1.53倍。这可能由于水溶液制备的氯化钠改性三聚氰胺前驱体的晶体结构的改变,引起煅烧后氮化碳结晶性的增强,进而有助于电荷的快速传输,使得光生载流子的分离效率增强,从而增强了其可见光催化性能。

熔盐法合成三钼酸钾超长纳米线及其生长机理研究

本文以硝酸锂-硝酸钠-硝酸钾三元硝酸盐为反应介质,以三氧化钼为原料,研究了反应温度、反应物/熔盐比例和清洗方式等因素对三钼酸钾纳米线制备的影响规律。进一步采用X射线衍射仪、扫描电子显微镜和透射电子显微镜对产物的结构和形貌进行表征。结果表明,在410℃反应40分钟,随后使用50%的乙醇冰水溶液洗涤,可以得到直径约200 nm、长径比超过2000的三钼酸钾超长纳米线。当反应温度低于160℃时,三氧化钼尚不能与熔盐反应。当反应温度高于170℃时,开始析出三钼酸钾纳米线。通过能谱分析可知,本研究中熔盐法制备的三钼酸钾纳米线的生长机理遵循溶解-析出的反应机制。降温过程中溶解的钼离子逐渐过饱和析出,进而与熔盐中的钾离子反应,形成三钼酸钾一维结构。

纳米级LiNi_(0.05)Mn_(1.95)O_(4)正极材料制备及电化学性能研究

为有效抑制尖晶石锰酸锂的Jahn-Teller效应,改善其在高倍率充放电循环中容量衰减快的问题,采取熔盐燃烧法和不同焙烧温度成功制得LiNi_(0.05)Mn_(1.95)O_(4)样品。实验结果表明,Ni掺杂和不同的焙烧温度没有改变LiMn_(2)O_(4)的晶体结构,随焙烧温度升高,结晶性增加,颗粒尺寸增大,逐渐由纳米级变为亚微米级。在优化焙烧温度650℃下制备的样品电化学性能最优,5C下初始放电比容量及500次循环后容量保持率分别为100.8 mA·h/g和80.0%,更高倍率(10C)下500次循环容量仅衰减7.5%。动力学性能测试结果表明,其具有较大锂离子扩散系数(3.26×10^(-16)cm^(2)/s)和较小表观活化能(25.67 kJ/mol)。Ni掺杂和不同的焙烧温度抑制了LiMn_(2)O_(4)材料的Jahn-Teller效应,提高了材料的倍率性能和循环寿命。