LaNi_(3.15-x)Mn_xCo_(0.25)Al_(0.1)储氢合金结构及电化学性能

为了研究Mn替代Ni对AB3.5型储氢合金结构及电化学性能的影响,采用电弧炉熔炼制备LaNi3.15-xMnxCo0.25Al0.1合金。采用XRD、SEM等材料分析方法以及恒电流充放电等电化学测试技术,研究LaNi3.15-xMnxCo0.25Al0.1(0≤x≤0.3)合金的结构和电化学储氢性能。结果表明:LaNi3.15-xMnxCo0.25Al0.1(0≤x≤0.3)合金由多相组合形成,合金的主相为LaNi5和La2Ni7;随着Mn替代Ni含量的增加,LaNi5相中a轴和c轴以及晶胞体积增加;合金电极的最大放电容量有所升高,由x=0的238mA·h/g逐渐增加到x=0.3的277.1mA·h/g;高倍率性能随着Mn含量的增加先升高后降低,在x=0.2时合金的高倍率性能最佳。     

Co部分替代Ni对La_(0.4)Er_(0.4)Mg_(0.2)Ni_(3.3-x)Co_xAl_(0.2)(0.1≤x≤0.4)储氢合金结构和电化学性能的影响

为了改善储氢合金La0.4Er0.4Mg0.2Ni3.3-xCoxAl0.2(0.1≤x≤0.4)的结构和综合电化学性能,采用Co部分替代Ni的方法,实验采用高频感应炉制备La0.4Er0.4Mg0.2Ni3.3-xCoxAl0.2(0.1≤x≤0.4)储氢合金。通过X射线衍射技术和电化学测量方法研究储氢合金的晶体结构和电化学性能。XRD图谱显示样品储氢合金主要由LaNi5和La2Ni7相组成,电化学实验表明,随着Co含量的增高,储氢合金电极的最大放电容量和50次循环后的容量保持率S50基本呈现增加状态,放电容量从x=0.1时的225mA·h/g升高到x=0.4时的254.9mA·h/g,容量保持率S50从57.11%(x=0.1)增加到66.10%(x=0.4),但高倍率性能不断下降。通过交流阻抗(EIS)和线性扫描(LS)对Co替代Ni的合金动力学性能分析发现,Co替代Ni后合金的表面电荷转移能力先降低后升高。     

A2B7型La0.75Mg0.25Ni3.5-xCrx(x=0～0.3)贮氢合金相结构及电化学性能研究

采用感应熔炼方法制备了La0.75Mg0.25Ni3.5-xCrx(x=0,0.05,0.1,0.2,0.3)四元贮氢合金,系统地研究了合金B端Cr元素对Ni部分替代对合金相结构及电化学性能的影响.X衍射(XRD)分析表明,La0.75Mg0.25Ni3.5合金是由La2Ni7相组成.随着Cr元素的加入,该类合金中出现LaNi5相及LaNi3相,且随着Cr含量的增加而增多.电化学测试表明,随Cr含量的增加,合金电极活化次数变化不大,最大放电容量逐步降低,合金的最大放电容量由x=0.05时的383.43 mAh/g下降到x=0.3时的348.40 mAh/g;而合金的高倍率放电性能呈现先增后减的趋势,当电流密度为900 mA/g时,合金的高倍率放电性能由83.66%(x=0)增加到92.57%(x=0.05)然后减小到83.9%(x=0.3);循环稳定性先增加后下降,当x=0.1时合金电极的循环寿命达到最大(S100=74.71%).     

储氢合金LaNi（4．2＋5x）Mn0．4A10．4Zrx的微观组织及电化学性能研究

研究了x(Zr)及热处理工艺对LaNi(4.2 5x)Mn0.4Al0.4Zrx储氢合金微观组织与电化学性能的影响．结果表明：添加Zr元素后该储氢合金中均出现Zr(Ni，A1，Mn)5第二相，并且第二相的含量随x的增大而增多．当x=0．4时，经热处理后合金中的第二相沿主相晶界呈网状分布，而且其韧性很好．由于第二相对主相起到了防腐蚀保护作用，并降低了充放电过程中晶格畸变引起的合金粉化的速度，从而使循环稳定性显著提高，但由于第二相不是吸氢相，对电化学容量没有贡献，因此它的出现使合金的放电容量降低．     

热处理温度对储氢合金高倍率放电性能的影响

研究了不同温度下的热处理对MLNi3.8Co0.75Mn0.4Al0.2储氢合金高倍率放电性能的影响.XRD测试结果表明热处理之后合金结晶度增加.电化学性能测试结果表明热处理明显改善了储氢合金电极的高倍率放电性能,在900 mA/g的放电电流下,经热处理的储氢合金电极的高倍率放电能力(HRD)均在80%以上,而原始合金电极在相同的放电条件下却不能放电.经过热处理提高了电极的交换电流密度,降低了电极的极化电阻,改善了电极在放电过程中的去极化作用.热处理温度在673 K时合金电极的交换电流密度最高,极化电阻值最低,高倍率放电性能最好.     

La1-xCexNi3.54Co0.78Mn0.35Al0.32贮氢合金相结构和电化学性能的研究

采用真空电弧熔炼和热处理方法制备了La1-xCexNi3.54Co0.78Mn0.35Al0.32(x=0.1,0.2,0.3,0.4,0.5,0.6)贮氢合金.X射线衍射(XRD)分析表明,合金含有单一CaCu5型六方结构相.电化学性能测试表明,随着x的增加,合金的最大放电容量从348.1mAh/g(x=0.1)单调地减小到310.1 mAh/g(x=0.6);HRD1200先从28.6%(x=0.1)增加到65.4%(x=0.5)然后降低到60.1%(x=0.6),归因于合金表面的电催化活性和合金体内氢原子扩散速率均随x的增大先增大后减小.     

La2Ca2Mg2Ni13-xCox贮氢合金的相结构和电化学性能

研究元素Co部分替代Ni对La2Ca2Mg2Ni13合金相结构和电化学性能的影响。结果表明,La2Ca2Mg2Ni13-xCox（x=0,0．25,0．5,0．75和1．0）系列合金主要由PuNi3型结构的（La,Ca,Mg）（Ni,Co）,相和CaCu5型结构的（La,Ca）（Ni,Co）,相组成,随合金中Co替代量x的增加,PuNi3型主相的含量先增加后降低。当x=0．75时,合金具有最高的放电容量360mA·h/g,并具有较好的循环稳定性。     

铸态及快淬态La2Mg(Ni0.85Co0.15)9Crx(x=0～0.4)贮氢合金的电化学性能

为了提高La-Mg-Ni系(PuNi3型)贮氢合金的电化学循环稳定性,在La2Mg(Ni0.85Co0.15)9合金中加入微量Cr,用铸造及快淬工艺制备了La2Mg(Ni0.85Co0.15)9Crx(x=0,0.1,0.2,0.3,0.4)贮氢合金.研究了Cr含量对铸态及快淬态合金微观结构及电化学性能的影响.XRD,SEM及TEM的分析结果表明,铸态及快淬态合金具有多相结构,包括(La,Mg)Ni3相(PuNi3型结构)、LaNi5相和一定量的LaNi2相.随Cr含量的增加,铸态合金中LaNi2相的量增加.电化学测试结果表明,Cr的加入提高了铸态及快淬态合金的循环稳定性,但使合金的容量下降.当Cr添加量从0增加到0.4时,铸态合金的容量从396.3 mAh/g下降到355.6 mAh/g,循环寿命从72次增加到97次;快淬态(30 m/s)合金的容量从364.2 mAh/g下降到334.2 mAh/g,循环寿命从100次增加到131次.Cr添加使铸态合金的放电电压特性和活化性能得到改善.     

多孔碳包覆硅微球于锂离子电池负极中的应用

为了缓解纯硅负极材料在充放电过程中带来的巨大体积效应并降低电解质与电极之间的副反应程度,提出了一种简单高效的硅碳复合材料合成方法.以P123为分散剂、葡萄糖为碳源,利用水热法制备P-Si/C复合材料.结果表明,制备得到的复合材料可以极大地缓解充放电过程中产生的体积效应.当复合材料作为锂电池负极时,其首次放电比容量为1 800 mA·h/g,在500 mA/g电流密度下经100次循环后,其放电比容量能够稳定维持为521 mA·h/g,呈现出良好的循环性能.     

表面改性对非晶态CeMg12合金电化学储氢性能的影响

研究了球磨时间、氟处理、表面包覆对CeMg12+200%Ni(质量分数,下同)复合贮氢合金电极电化学性能的影响.结果表明球磨50 h后的复合电极材料的具有最大的电化学放电容量为1 209.6 mAh/g,但是电化学循环稳定性较差,10次循环保持率为37.3%;氟处理后复合电极的最大放电容量和循环稳定性同时下降;添加质量分数4%Ti进行球磨包覆后,合金的最大放电容量基本上不变,为1 049.58 mAh/g,而10次循环的保持率提高到了53.7%.另外,将复合电极置于Hg中浸泡也可以提高循环稳定性.     

Ba3La2Ti2Ta2O15: A new microwave dielectric of A5B4O15-type cation-deficient perovskites

The synthesis, structure and properties of a new A5B4O15-type cation-deficient perovskite Ba3La2Ti2Ta2O15 were discribed. The compound was prepared by the conventional solid-state reaction route. The phase and structure of the ceramics were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）. The results reveal that the compound is successfully synthesized. The compound crystallizes in the trigonal system with unit cell parameter a=5.6730（2） A, c=11.6511（2） A, V=324.93（1） A^3 and Z=1. The microwave dielectric properties of the ceramic are studied using a network analyzer, and it shows a high dielectric constant of 45.1, a high quality factors with Q×fof21 029 GHz, and a positive τf of 5.3 ppm℃^-1.     

低介Ba(Al0.98Co0.02)2Si2O8-Ba5Si8O21基LTCC微波介质陶瓷的研究

采用传统固相反应法,按摩尔比合成0.7Ba(Al_0.98Co_0.02)₂Si₂O₈?0.3Ba₅Si₈O₂₁(BACS-BS)基陶瓷,分析Li₂O-B₂O₃(1wt%)(L-B)烧结助剂对其烧结特性、相组成和微波介电性能的影响,探讨0.7BACS-0.3BS+1wt%(L-B)陶瓷理论与实验介电常数(ε_r)的差异。结果表明:添加1wt%(L-B)烧结助剂能有效降低0.7BACS-0.3BS基陶瓷的烧结温度(950 ℃),但严重影响其微波介电性能;在950℃烧结的0.7Ba(Al_0.98Co_0.02)₂Si₂O₈-0.3Ba₅Si₈O₂₁+1wt%(Li₂O-B₂O₃)陶瓷具有较好的微波介电性能,其ε_r=7.56, Q×f=13 976 GHz, τ_f=?6.32 ppm/℃;0.7BACS-0.3BS+1wt%(L-B)复合陶瓷与Ag电极有很好的化学相容性,这为其在LTCC技术的应用奠定了良好的基础。     

Electrical conductivity of （Na3AlF6-40%K3AlF6）-AlF3-Al2O3 melts

The effects of contents of AlF3 and Al2O3, and temperature on electrical conductivity of （Na3AlF6-40%K3AlF6）- AlF3-Al2O3 were studied by continuously varying cell censtant （CVCC） technique. The results show that the conductivities of melts increase with the increase of temperature, but by different extents. Every increasing 10 ℃ results in an increase of 1.85 × 10^-2, 1.86× 10^-2, 1.89 × 10^-2 and 2.20 × 10^-2 S/cm in conductivity for the （Na3AlF6-40%K3AlF6）-AlF3 melts containing 0%, 20%, 24%, and 30% AlF3, respectively. An increase of every 10 ℃ in temperature results an increase about 1.89× 10^-2, 1.94 × 10^-2, 1.95 × 10^-2, 1.99× 10^-2 and 2.10× 10^-2 S/cm for （Na3AlF6-40%K3AlF6）-AlF3-Al2O3 melts containing 0%, 1%, 2%, 3% and 4% Al2O3, respectively. The activation energy of conductance was calculated based on Arrhenius equation. Every increasing 1% of AlF3 results in a decrease of 0.019 and 0.020 S/cm in conductivity for （Na3AlF6-40%K3AlF6）-AlF3 melts at 900 and 1 000 ℃, respectively. Every increase of 1% Al2O3 results in a decrease of 0.07 S/cm in conductivity for （Na3AlF6-40%K3AlF6）-AlF3-Al2O3 melts. The activation energy of conductance increases with the increase in content of AlF3 and Al2O3.     

Preparation and electrical-magnetic properties of Co0.6Cu0.16Ni0.24Fe2O4/MWCNTs composites

Co0.6Cu0.16Ni0.24Fe2O4/multi-walled carbon nanotube nanocomposites (CCNF/MWCNTs) were synthesized by solution filling method.The phase structure,thermal stability,morphology and electrical-magnetic properties of the samples were characterized by means of modern testing technology.The effect of iron concentration,filling time,sintering temperature on their electrical and magnetic performance was discussed.The results indicated that conductivity was related to the content of MWCNTs,while the magnetism correlated with the volume fraction of the filled CCNF in the composites.When the optimal condition satisfied the filling time of 18 h,ferric concentration of 0.25 mol L-1 and sintering temperature of 350°C,the prepared composite had the best magnetic loss performance,and its minimum reflection loss reached-22.47 dB on 9.76 GHz,the available bandwidth was beyond 2.0 GHz.Hence,the obtained composite can be used as advancing absorption and shielding material due to its favorable microwave absorbing property.     

Ca0.9Ce0.1Ti0.8Al0.2SiO5在水热作用下的化学稳定性

通过固相法合成掺铈榍石固溶体(Ca0.9 Ce0.1Ti0.8Al0.2SiO5),采用PCT粉末浸泡试验法,借助X射线衍射(XRD)、扫描电镜(SEM)、电感耦合等离子体发射光谱(ICP-OES)等分析测试手段,研究掺铈榍石固溶体在热液作用下的稳定性.实验结果表明,掺铈榍石固化体在不同条件下(温度150～ 200℃,0.476～1.554 MPa,pH值5～9),都具有良好的稳定性.随着浸泡时间的增加,各元素的归一化浸出率逐渐降低并保持在较低水平.     

Synthesis and characterization of Mg3(PO4)2-coated Li1.05Ni1/3Mn1/3Co1/3O2 cathode material for Li-ion battery

Mg₃(PO₄)₂-coated Li_1.05Ni_1/3Mn_1/3Co_1/3O₂ cathode materials were synthesized via co-precipitation method. The morphology, structure, electrochemical performance and thermal stability were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), cyclic voltammetry(CV), electrochemical impedance spectroscopy(EIS), charge/discharge cycling and differential scanning calorimeter (DSC). SEM analysis shows that Mg₃(PO₄)₂-coating changes the morphologies of their particles and increases the grains size. XRD and CV results show that Mg₃(PO₄)₂-coating powder is homogeneous and has better layered structure than the bare one. Mg₃(PO₄)₂-coating improved high rate discharge capacity and cycle-life performance. The reason why the cycling performance of Mg₃(PO₄)₂-coated sample at 55 °C was better than that of room temperature was the increasing of lithium-ion diffusion rate and charge transfer rate with temperature rising. Mg₃(PO₄)₂-coating improved the cathode thermal stability, and the result was consistent with thermal abuse tests using Li-ion cells: the Mg₃(PO₄)₂ coated Li_1.05Ni_1/3Mn_1/3Co_1/3O₂ cathode did not exhibit thermal runaway with smoke and explosion, in contrast to the cells containing the bare Li_1.05Ni_1/3Mn_1/3Co_1/3O₂. Funded by the National Natural Science Foundation of China (No. 20273047)     

Modification of LiCo1/3Ni1/3Mn1/3O2 cathode material by CeO2-coating

LiCo_1/3Ni_1/3Mn_1/3O₂ was coated by a layer of 1.0 wt% CeO₂ via sol-gel method. The bared and coated LiMn_1/3Co_1/3Ni_1/3O₂ was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), cyclic voltammogram (CV) and galvanotactic charge-discharge test. The results show that the coating layer has no effect on the crystal structure, only coating on the surface; the 1.0 wt% CeO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ exhibits better discharge capacity and cycling performance than the bared LiCo_1/3Ni_1/3Mn_1/3O₂. The discharge capacity of 1.0 wt% CeO₂-coated cathode is 182.5 mAh·g⁻¹ at a current density of 20 mA·g⁻¹, in contrast to 165.8 mAh·g⁻¹of the bared sample. The discharge capacity retention of 1.0 wt% CeO₂-coated sample after 12 cycles reaches 93.2%, in comparison with 86.6% of the bared sample. CV results show that the CeO₂ coating could suppress phase transitions and prevent the surface of cathode material from direct contact with the electrolyte, thus enhance the electrochemical performance of the coated material.     

Electrolysis expansion performance of semigraphitic cathode in [K3AlF6/Na3AlF6]-AlF3-Al2O3 bath system

The electrolysis expansion of semigraphitic cathode in [K₃AlF₆/Na₃AlF₆]-AlF₃-Al₂O₃ bath system was tested by self-made modified Rapoport apparatus. A mathematical model was introduced to discuss the effects of α _CR (cryolite ratio) and β _KR (elpasolite content divided by the total amount of elpasolite and sodium cryolite) on performance of cathode electrolysis expansion. The results show that K and Na (potassium and sodium) penetrate into the cathode together and have an obvious influence on the performance of cathode electrolysis expansion. The electrolysis expansion and K/Na penetration rate increase with the increase of α _CR. When α _CR=1.9 and β _KR=0.5, the electrolysis expansion is the highest, which is 3.95%; and when α _CR=1.4 and β _KR=0.1, the electrolysis expansion is the lowest, which is 1.28%. But the effect of β _KR is correlative with α _CR. When α _CR=1.6 and 1.9, with the increase of β _KR, the electrolysis expansion and K/Na penetration rate increase. However, when α _CR=1.4, the electrolysis expansion and K/Na penetration rate firstly increase and then decrease with the increase of β _KR. Foundation item: Project (2005CB623703) supported by the Major State Basic Research and Development Program of China; Project (2008AA030502) supported by the National High-Tech Research and Development Program of China     

Characteristics of LiCoO2, LiMn2O4 and LiNi0.45Co0.1Mn0.45O2 as cathodes of lithium ion batteries

LiNi_0.45Co_0.10Mn_0.45O₂ was synthesized from Li₂CO₃ and a triple oxide of nickel, cobalt and manganese at 950 °C in air. The structures and characteristics of LiNi_0.45Co_0.10Mn_0.45O₂, LiCoO₂ and LiMn₂O₄ were investigated by XRD, SEM and electrochemical measurements. The results show that LiNi_0.45Co_0.10Mn_0.45O₂ has a layered structure with hexagonal lattice. The commercial LiCoO₂ has sphere-like appearance and smooth surfaces, while the LiMn₂O₄ and LiNi_0.45Co_0.10Mn_0.45O₂ consist of cornered and uneven particles. LiNi_0.45Co_0.10Mn_0.45O₂ has a large discharge capacity of 140.9 mA · h/g in practical lithium ion battery, which is 33.4% and 2.8% above that of LiMn₂O₄ and LiCoO₂, respectively. LiCoO₂ and LiMn₂O₄ have higher discharge voltage and better rate-capability than LiNi_0.45Co_0.10Mn_0.45O₂. All the three cathodes have excellent cycling performance with capacity retention of above 89.3% at the 250th cycle. Batteries with LiMn₂O₄ or LiNi_0.45Co_0.10Mn_0.45O₂ cathodes show better safety performance under abusive conditions than those with LiCoO₂ cathodes. Foundation item: Project(50302016) supported by the National Natural Science Foundation of China; Project(2005037698) supported by the Postdoctoral Science Foundation of China     

Molar heat capacities of La2Mo2O9 and La1.9Sr0.1MO209-δ

The molar heat capacities of La2Mo209 and La1.9Sr0.1MO209-δ were obtained using the differential scanning calorimetry （DSC） technique in a temperature range from 298 to 1473 K. The DSC curve of La2Mo209 showed an endothermal peak around 834 K corresponding to a first-order monoclinic-cubic phase transition, and the enthalpy change accompanying this phase transition is 5.99 kJ/mol. No evident endothermal peak existed in the DSC curve of La1.9Sr0.1MO209-δ, but a broad thermal anomaly existed in its heat capacity curve at around 832 K. In addition, the heat capacity values of La2Mo209 and La1.9Sr0.1MO209-δ began to decrease at 1196 and 1330 K, respectively. The non-transitional heat capacity values of La2Mo209 and La1.9Sr0.1MO209-δ were formulated using multiple regression analysis in two temperature ranges.