退火温度对La0.8Mg0.2Ni3.3Co0.2Six(x=0、0.1)合金电化学贮氢性能的影响

采 用 真 空 感 应 熔 炼 制 备 了La0.8Mg0.2Ni3.3Co0.2Six(x=0、0.1)电极合金,并将铸态合金进行真空退火处理,退火温度为900、950、1000和1050℃,保温时间为8h。用XRD分析了铸态及退火态合金的相结构,测试了铸态及退火态合金的电化学贮氢性能。结果表明,铸态及退火态合金均具有多相结构,包括两个主相(La,Mg)2Ni7和LaNi5以及一个残余相LaNi3。退火处理未改变合金的相组成,但使两个主相的含量发生明显改变。合金主相的晶格常数及晶胞体积随退火温度的增加而增加。铸态及退火态合金均具有良好的活化性能,第1次循环即可达到最大放电容量。退火处理明显改善了合金的电化学循环稳定性,合金的放电容量随退火温度的升高先增加后减小。合金的高倍率放电性能(HRD)、电化学交流阻抗谱(EIS)以及氢扩散系数(D)的测试表明,合金的电化学动力学随退火温度的升高先上升后降低。     

添加Si对La-Mg-Ni系A2B7型电极合金循环稳定性的影响

为了改善La-Mg-Ni系A2B7型电极合金的电化学循环稳定性,在合金中添加少量Si。采用真空感应熔炼制备了La0.8Mg0.2Ni3.3Co0.2Si x(x=0~0.2)电极合金,并将部分合金在真空条件下,温度为900、950、1000和1050℃下进行了退火处理。用XRD、SEM分析了铸态及退火态合金的微观结构,测试了铸态及快淬态合金的电化学循环稳定性。结果表明,铸态及快淬态合金均具有多相结构,包括两个主相(La,Mg)2Ni7和LaNi5及一个残余相LaNi3。添加Si使LaNi5相增加而(La,Mg)2Ni7相减少。合金的电化学循环稳定性随Si含量的增加而增加,当Si含量x从0增加到0.2时,铸态合金100次充放循环后的容量保持率(S100)从64.2%增加到73.1%,而950℃退火态合金的S100值从80.3%增加到93.7%。     

La2-xMgxNi7.0(x=0.4,0.5,0.6,0.7,0.8)贮氢合金结构和电化学性能的研究

用高频感应熔炼的方法制备了La2-xMgxNi7.0(x=0.4,0.5,0.6,0.7,0.8)贮氢电极合金,采用x-ray衍射和XRD粉末衍射全谱拟合分析方法及电化学方法系统研究了随Mg含量的增加,该类合金相结构和电化学性能的变化规律,以及合金在不同退火温度(1123K,1203K,1253K)和不同退火时间(24h,72h,144h)下相结构和微观组织及电化学性能的变化规律.实验结果表明,该类合金由(La,Mg)2Ni7相(Ce2Ni7型结构)、LaNi5(CaCu5型结构)相、(La,Mg)Ni3相(PuNi3型结构)及少量未知相组成.随Mg含量的增加,电极电化学放电容量呈先升高后降低趋势,当x=0.6时达到最大值389.87mAh/g;当Mg含量进一步增加时,电化学放电容量迅速降低,x=0.8时电化学放电容量为188.34mAh/g;随Mg含量的增加,合金组织中(La,Mg)Ni3相和LaNi5相增多.退火处理很大程度上消除了LaNi5相,高温退火有利于(La,Mg)2Ni7相的生成,低温退火有利于(La,Mg)Ni3相生成.退火时间的延长对合金相结构影响不明显,但提高了合金组织均匀性,同时使电化学放电容量降低.不同的退火温度和退火时间对未知相影响不明显.本文研究表明,退火温度对(La,Mg)2Ni7合金相结构有重要影响,Mg含量是影响合金相结构和电化学放电容量的关键.     

退火温度对Mm（NiCoMnAl）5/5wt%Mg2Ni储氢合金结构和电化学性能的影响

采用二步熔炼法制备了Mm(NiCoMnAl)5/5%(质量分数)Mg2Ni复合储氢合金,并对其在不同温度(1023、1123和1223K)下进行退火热处理10h。用X射线衍射(XRD)、扫描显微镜(SEM)和电化学测试方法研究了退火温度对合金结构和电化学性能的影响。结果表明,铸态Mm(NiCoMnAl)5/5%(质量分数)Mg2Ni复合合金由LaNi5相和少量的Mg2Ni相组成,而退火态合金由LaNi5相和(La,Mg)Ni3新相组成。合金的最大放电容量和高倍率放电性能随退火温度的升高呈现出先增强后减弱的变化规律,其中退火温度为1023K时,合金电极的上述性能均达到最佳。合金的容量保持率随退火温度的升高而单调地增大,60次充放电循环后容量保持率从铸态合金的86.6%增大到退火合金(1223K)的92.4%。     

退火对La0.75Mg0.25Ni3.5Cox（x=0，0.6）合金结构与电化学性能影响

为了改善La0.75Mg0.25Ni3.5Cox(x=0,0.6)合金电极的循环稳定性,对铸态合金在0.3MPa压力氩气保护下进行不同温度退火(1123、1223和1323K),保温时间均为10h.研究了退火温度对合金电化学性能的影响.X射线衍射(XRD)和扫描电镜(SEM)分析表明,铸态及1123K温度退火后合金主要由LaNi5、(La,Mg)2Ni7相及少量LaNi2相组成;退火温度为1223和1323K时,合金中LaNi2相消失,合金主要由LaNi5、(La,Mg)Ni3及(La,Mg)2Ni7相组成.电化学试验结果表明,随着退火温度增加,x=0及x=0.6的合金最大放电容量分别从铸态的343.7、319.2增加到1323K时的390.4、357.5mAh/g;同时退火改善合金的循环稳定性,100次充放电循环后,随着退火温度升高,x=0、0.6时合金的容量保持率(S100)分别从铸态的55.17%、58.22%增加到1323K时的76.66%、67.58%.     

铸态及退火态La（0.75）Mg（0.25）Ni（3.5）Si（0.10）储氢合金相结构和高温电化学性能的研究

研究了铸态及退火（940℃、8h）La0.75Mg0.25Ni3.5Si0.10储氢合金相结构,及在30、45、55和70℃环境温度下电化学性能,包括放电容量、寿命、高倍率和自放电行为。X射线衍射分析表明,两合金均为La-Ni5、（La,Mg）2Ni7和（La,Mg）Ni3相组成的多相结构,退火处理使LaNi5和（La,Mg）Ni3相减少,（La,Mg）2Ni7相增多,但两合金主相均为LaNi5。研究发现,铸态和退火态合金活化性能都较优异,最大放电容量均随测试温度升高而减小,并且退火处理能提高每个温度点的放电容量,70℃高温下最为显著,合金放电容量从238.4mAh/g增加到342.5mAh/g。随温度升高,铸态合金的高倍率放电性先增大后减小,而退火合金高倍率放电性随温度升高单调增加。合金的荷电保持率随温度升高而降低,退火处理可提高各个温度点的荷电保持率。     

退火温度对Mm(NiCoMnAl)5/5%(质量分数)Mg2Ni储氢合金结构和电化学性能的影响

采用二步熔炼法制备了Mm(NiCoMnAl)5/5%(质量分数)Mg2Ni复合储氢合金,并对其在不同温度(1023、1123和1223K)下进行退火热处理10h。用X射线衍射(XRD)、扫描显微镜(SEM)和电化学测试方法研究了退火温度对合金结构和电化学性能的影响。结果表明,铸态Mm(NiCoMnAl)5/5%(质量分数)Mg2Ni复合合金由LaNi5相和少量的Mg2Ni相组成,而退火态合金由LaNi5相和(La,Mg)Ni3新相组成。合金的最大放电容量和高倍率放电性能随退火温度的升高呈现出先增强后减弱的变化规律,其中退火温度为1023K时,合金电极的上述性能均达到最佳。合金的容量保持率随退火温度的升高而单调地增大,60次充放电循环后容量保持率从铸态合金的86.6%增大到退火合金(1223K)的92.4%。     

La-Mg-Ni基(PuNi3型)贮氢合金的微观结构与电化学性能

用铸造及快淬工艺制备了La Mg Ni 系(PuNi3 型)贮氢合金La2Mg(Ni0.85 Co0.15)9Bx(x=0、0.1、0.2),分析测试了铸态及快淬态合金的微观结构与电化学性能,研究了硼及快淬工艺对合金微观结构及电化学性能的影响。结果表明,铸态合金具有多相结构,主相包括(La, Mg)Ni3 相和LiNi5 相,残余相为一定量的LaNi2 相和微量的Ni2B相,经快淬处理后Ni2B相消失,并且其它相的相对量随淬速的变化而变化。硼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。不含硼合金的容量随淬速的增加而单调减小,含硼合金的容量随淬速变化有一个极大值。合金的循环寿命随淬速的增加而增加,铸态及快淬态合金均有优良的活化性能。     

烧结工艺对贮氢合金La0.67Mg0.33Ni2.5Co0.5的微观组织结构及电化学性能影响的研究

系统研究了固相反应烧结方法制备La0.67Mg0.33Ni2.5Co0.5贮氢合金的烧结工艺对该合金的微观组织结构及电化学性能的影响规律.分析和研究了合金的微观组织结构、电化学放电性能及Mg含量的挥发损失问题.XRD和SEM及EPMA分析结果表明,在不同烧结条件下合金均由不合Mg的LaNi5相、富Mg的LaNi3相及一个贫Mg的LaNix(x=3.0～3.8)相三相组成.当烧结温度不超过1203k时合金主相为LaNi3相,当烧结温度超过1203K,LaNi5相逐步成为主相.原子吸收光谱分析结果表明,烧结温度不超过1203K,Mg元素没有明显损失;当烧结温度超过1203K,会引起Mg的大量挥发损失.电化学性能分析结果表明,烧结温度不超过1203K,合金放电能力主要受合金组织形成与均匀性影响;而烧结温度超过1203K,Mg元素挥发损失成为影响合金放电能力的决定因素.烧结条件为873～1123k保持24h、1203k保持2h,是制备La0.67Mg0.33Ni2 5Co0.5贮氢合金的适宜工艺.用该工艺制备的La0 67Mg0.33Ni2.5Co0.5贮氢合金Mg含量稳定(2.92%质量分数)、微观组织均匀、放电容量高(395mAh/g)、活化性能好(2个循环).     

铸态和退火态A2B7型La-Mg-Ni系合金的电化学研究（英文）

为了改善铸态La3MgN i14合金的电化学性能,在0.3 MPa氩气气氛下对La3MgN i14合金进行了10 h退火处理,退火温度分别为1 123,1 223和1 323 K。采用X射线衍射(XRD)、扫描电镜(SEM)和电化学实验研究了合金的微观结构和电化学性能。结果表明,铸态及1 123 K温度退火后的合金由LaN i5相、(La,Mg)2N i7相以及少量的LaN i2相组成。1 223 K温度退火后合金含有LaN i5,(La,Mg)2N i7和(La,Mg)N i3相。1 323 K温度退火后合金的主相为LaN i5和(La,Mg)N i3相。与铸态合金相比,退火后合金组织更加均匀,晶粒长大。随着退火温度的增加,合金的一些电化学性能(如最大放电容量、放电效率、循环稳定性)以及动力学参数(如高倍率放电性能)增强,而电位差和电荷迁移电阻降低。在本研究范围内,为了放电容量和循环稳定性之间的平衡,铸态La3MgN i14合金的适宜退火温度为1 323 K。     

钙钛矿型(La0.2Li0.2Ba0.2Sr0.2Ca0.2)TiO3高熵氧化物陶瓷的制备及性能研究

高熵陶瓷是近年来在高熵合金基础上逐渐发展起来的一种新的陶瓷材料体系, 它的出现为开发具有优异性能的非金属材料提供了新的理念和路线。本研究采用固相烧结法制备A位等摩尔比的钙钛矿型高熵氧化物陶瓷(La_0.2Li_0.2Ba_0.2Sr_0.2Ca_0.2)TiO₃, 并探索了烧结温度对高熵陶瓷的物相结构及电学性能的影响。结果表明, 陶瓷经现有温度烧结后均表现为立方钙钛矿结构, 并且展现出良好的绝缘性, 其漏电流密度在10^-8~10^-6 A/cm²数量级。尽管随烧结温度的升高, 陶瓷的晶粒尺寸不断增大, 但该显微结构与介电性能的关联并不显著。当烧结温度为1350 ℃时, 介电常数出现最大值, 在频率为100 Hz下, 介电常数约为230。同时, 该高熵陶瓷的介电温谱表明陶瓷存在弛豫行为, 其介电常数的弛豫峰随着频率的增加向高温方向移动。     

(Sm0.2Gd0.2Dy0.2Y0.2Yb0.2)3TaO7高熵陶瓷的制备及热物理性能

寻求具有良好热物理性能的新型陶瓷材料是热障涂层领域的研究热点之一。本研究采用固相反应法制备了(Sm_0.2Gd_0.2Dy_0.2Y_0.2Yb_0.2)₃TaO₇高熵陶瓷材料, 对其晶体结构、显微组织、元素分布、结构稳定性和热物理性能进行了研究。结果表明: 制备的高熵陶瓷具有单一的缺陷萤石结构, 元素分布均匀, 晶粒尺寸在0.2~3 μm之间。经高温循环热处理后依然保持单一的萤石结构, 表现出良好的高温结构稳定性。25~800 ℃范围内热导率为0.72~0.74 W/(m?K), 远低于7YSZ, 1200 ℃下的热膨胀系数约为5.6×10^-6K^-1, 低于热障涂层(TBCs)对表面陶瓷层材料的要求, 但与环境障涂层(EBCs)硅基陶瓷基体的热膨胀系数((3.4~5.5)×10^-6K^-1)接近。     

High porosity and low thermal conductivity high entropy (Zr0.2Hf0.2Ti0.2Nb0.2Ta0.2)C

Porous ultra-high temperature ceramics (UHTCs) are promising for ultrahigh-temperature thermal insulation applications. However, the main limitations for their applications are the high thermal conductivity and densification of porous structure at high temperatures. In order to overcome these obstacles, herein, porous high entropy (Zr_0.2Hf_0.2Ti_0.2Nb_0.2 Ta_0.2)C was prepared by a simple method combing in-situ reaction and partial sintering. Porous high entropy (Zr_0.2Hf_0.2Ti_0.2Nb_0.2Ta_0.2)C possesses homogeneous microstructure with grain size in the range of 100–500 nm and pore size in the range of 0.2–1 μm, which exhibits high porosity of 80.99%, high compressive strength of 3.45 MPa, low room temperature thermal conductivity of 0.39 W·m⁻¹ K⁻¹, low thermal diffusivity of 0.74 mm²·s⁻¹ and good high temperature stability. The combination of these properties renders porous high entropy (Zr_0.2Hf_0.2Ti_0.2Nb_0.2Ta_0.2)C promising as light-weight ultrahigh temperature thermal insulation materials.     

High-entropy(Ca0.2Sr0.2Ba0.2La0.2Pb0.2)TiO3 perovskite ceramics with A-site short-range disorder for thermoelectric applications

Novel high-entropy perovskite-type(Ca0.2Sr0.2Ba0.2La0.2Pb0.2)TiO3(CSBLP)ceramics with cubic structure of Pm-3m space group were successful prepared by solid-sta...     

(Cr0.2Mn0.2Fe0.2Co0.2Mo0.2)B:A novel high-entropy monoboride with good electromagnetic interference shielding performance in K-band

A novel equimolar high-entropy(HE)transition metal monoboride,(Cr0.2Mn0.2Fe0.2Co0.2Mo0.2)B,was designed and prepared in powder and bulk form by high temperature elemental reac-tion method and spark plasma sintering(SPS)method,respectively.XRD analysis shows that HE(Cr0.2Mn0.2Fe0.2Co0.2Mo0.2)B possesses orthorhombic structure with Pnma space group.Through Rietveld refinement,the lattice parameters of HE(Cr0.2Mn0.2Fe0.2Co0.2Mo0.2)B are a=5.6675,b=2.9714,c=4.2209 and the theoretical density is 6.95 g/cm3.The Vickers hardness and electrical conductivity of HE(Cr0.2Mn0.2Fe0.2Co0.2Mo0.2)B bulk with relative density of 90％is 12.3±0.5 GPa and 0.49±0.04×106 S/m,respectively.Due to high electrical conductivity,HE(Cr0.2Mn0.2Fe0.2Co0.2Mo0.2)B bulk with 3.0 mm thickness displays superior EMI shielding performance in 18.0-26.5 GHz(K-band),and the average values of SET,SER,and SEA are 23.3 dB,13.9 dB,and 9.4 dB,respectively.The EMI shielding mechanism of HE(Cr0.2Mn0.2Fe0.2Co0.2Mo0.2)B mainly results from reflection.     

Porous high entropy (Zr0.2Hf0.2Ti0.2Nb0.2Ta0.2)B2: A novel strategy towards making ultrahigh temperature ceramics thermal insulating

Transition metal diborides based ultrahigh temperature ceramics (UHTCs) are characterized by high melting point, high strength and hardness, and high electrical and thermal conductivity. The high thermal conductivity arises from both electronic and phonon contributions. Thus electronic and phonon contributions must be controlled simultaneously in reducing the thermal conductivity of transition metal diborides. In high entropy (HE) materials, both electrons and phonons are scattered such that the thermal conductivity can significantly be reduced, which opens a new window to design novel insulating materials. Inspired by the high entropy effect, porous HE (Zr_0.2Hf_0.2Nb_0.2Ta_0.2Ti_0.2)B₂ is designed in this work as a new thermal insulting ultrahigh temperature material and is synthesized by an in-situ thermal borocarbon reduction/partial sintering process. The porous HE (Zr_0.2Hf_0.2Nb_0.2Ta_0.2Ti_0.2)B₂ possesses high porosity of 75.67%, pore size of 0.3–1.2 μm, homogeneous microstructure with small grain size of 400–800 nm, which results in low room temperature thermal diffusivity and thermal conductivity of 0.74 mm² s⁻¹ and 0.51 W m⁻¹ K⁻¹, respectively. In addition, it exhibits high compressive strength of 3.93 MPa. The combination of these properties indicates that exploring porous high entropy ceramics such as porous HE (Zr_0.2Hf_0.2Nb_0.2Ta_0.2Ti_0.2)B₂ is a novel strategy in making UHTCs thermal insulating.     

Temperature Dependent Thermal and Elastic Properties of High Entropy (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2: Molecular Dynamics Simulation by Deep Learning Potential

High entropy diborides are new categories of ultra-high temperature ceramics,which are believed promising candidates for applications in hypersonic vehicles.However,knowledge on high temperature thermal and mechanical properties of high entropy diborides is still lacking unit now.In this work,variations of thermal and elastic properties of high entropy (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 with respect to temperature were predicted by molecular dynamics simulations.Firstly,a deep learning potential for Ti-Zr-Hf-Nb-Ta-B diboride system was fitted with its prediction error in energy and force respectively being 9.2 meV/atom and 208 meV/(A),in comparison with first-principles calculations.Then,temperature dependent lattice constants,anisotropic thermal expansions,anisotropic phonon thermal conductivities,and elastic properties of high entropy (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 from 0 ℃ to 2400 ℃ were evaluated,where the predicted room temperature values agree well with experimental measurements.In addition,intrinsic lattice distortions of (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 were analyzed by displacements of atoms from their ideal positions,which are in an order of 10-3 (A) and one order of magnitude smaller than those in (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C.It indicates that lattice distortions in (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 is not so severe as expected.With the new paradigm of machine learning potential,deep insight into high entropy materials can be achieved in the future,since the chemical and structural complexly in high entropy materials can be well handled by machine learning potential.     

Effect of reaction routes on the porosity and permeability of porous high entropy(Y_(0.2)Yb_(0.2)Sm_(0.2)Nd_(0.2)Eu_(0.2))B_6 for transpiration cooling

Transpiration cooling technique is a reusable and high-efficiency thermal protection system(TPS), which is potential to improve the reusability and security of re-entry space vehicle. Relatively low density, high permeability and high porosity are general requirements for porous media of transpiration cooling systems. In this work, a new porous high entropy metal hexaboride(Y_(0.2)Yb_(0.2)Sm_(0.2)Nd_(0.2)Eu_(0.2))B_6 is designed and prepared by the in-situ reaction/partial sintering method. Two reaction routes are designed to synthesize(Y_(0.2)Yb_(0.2)Sm_(0.2)Nd_(0.2)Eu_(0.2))B_6, including boron thermal reduction and borocarbon thermal reduction.The as-prepared porous HE(Y_(0.2)Yb_(0.2)Sm_(0.2)Nd_(0.2)Eu_(0.2))B_6 ceramics possess homogeneous microstructure and exhibit low density, high porosity, high compressive strength and high permeability. The combination of these properties makes porous HE(Y_(0.2)Yb_(0.2)Sm_(0.2)Nd_(0.2)Eu_(0.2))B_6 promising as a candidate porous media for various transpiration cooling applications.