(Ti0.2V0.2Cr0.2Nb0.2Ta0.2)2AlC–(Ti0.2V0.2Cr0.2Nb0.2Ta0.2)C high-entropy ceramics with low thermal conductivity

In recent years, the microstructure and physicochemical properties of high-entropy ceramics have received much interest by the combination of multiple principal elements. Herein, (Ti_0.2V_0.2Cr_0.2Nb_0.2Ta_0.2)₂AlC–(Ti_0.2V_0.2Cr_0.2Nb_0.2Ta_0.2)C high-entropy ceramics (M₂AlC-MC HECs) were prepared by the spark plasma sintering (SPS) technique, attributing to the structural and chemical diversity of MAX phases. The microstructure of M₂AlC-MC HECs was characterized from micron to atomic scales, and the phase composition of M₂AlC-MC HECs was analyzed by a combination of Maud and Rietveld analysis. The results indicate the successful solid solution of Ti, V, Cr, Nb, and Ta atoms in the M-site of the 211-MAX configuration, and all the samples show a classic layered structure. The weight percentage of (Ti_0.2V_0.2Cr_0.2Nb_0.2Ta_0.2)₂AlC in the M₂AlC-MC HECs was more than 90%. Furthermore, the thermoelectric properties of M₂AlC-MC HECs were investigated for the first time in this study, and the electrical conductivity and thermal conductivity of HECs are 3278 S cm⁻¹ and 2.78 W m⁻¹ K⁻¹at 298 K, respectively.     

Oxyacetylene ablation of (Hf0.2Ti0.2Zr0.2Ta0.2Nb0.2)C at 1350 − 2050 °C

Ablation resistance of a multi-component carbide (Hf_0.2Ti_0.2Zr_0.2Ta_0.2Nb_0.2)C (HTZTNC) was investigated using an oxyacetylene flame apparatus. When the surface temperature of the HTZTNC was below 1800 °C, (Nb, Ta)₂O₅, (Hf, Zr)TiO₄, and (Hf, Zr)O₂ were found to be the main oxidation products, while at higher temperature, formation of (Hf, Zr, Ti, Ta, Nb)O_x was favored and its content gradually increased with the increase in ablation temperature. Based on the ablation results and thermodynamic simulation analysis, a possible ablation mechanism of HTZTNC was proposed. Active oxidation of TiC and outward diffusion of TiO were demonstrated to occur during the ablation process, which constitute the critical steps for the ablation of HTZTNC. These results can contribute to the design of ablation resistant ultra-high-temperature ceramics.     

Porous (Ce0.2Zr0.2Ti0.2Sn0.2Ca0.2)O2-δ high-entropy ceramics with both high strength and low thermal conductivity

Single-phase (Ce_0.2Zr_0.2Ti_0.2Sn_0.2Ca_0.2)O_2-δ porous high-entropy ceramics have been in-situ fabricated by foam-gelcasting-freeze drying method at different temperatures. The microstructure, phase composition, and properties of the obtained ceramics were investigated. The results indicate that compared with other porous ceramics reported in the literatures, this type of ceramics exhibits excellent performance. The sample prepared at 1350 °C shows high porosity (88.6 %), low thermal conductivity (0.023 W m^-1 K^-1), and high compressive strength (1.48 MPa). The current study suggests that porous (Ce_0.2Zr_0.2Ti_0.2Sn_0.2Ca_0.2)O_2-δ high entropy ceramics are promising candidates for thermal insulation applications.     

Effect of the reactive surface area of proton-conducting NiBa0.8Sr0.2Ce0.6Zr0.2Y0.2O3-δ anodes on cell performance

To determine the optimal combination of NiO and Ba_0.8Sr_0.2Ce_0.6Zr_0.2Y_0.2O_3-δ (BSCZY) for fabricating anode materials, Ni-BSCZY samples were prepared using the solid state reaction process. The porous structure of anode substrates not only provides mechanical strength to the fuel cells to enable fuel gases to flow to the electrolyte membrane but also creates an excess surface area on which to form a larger triple-phase boundary when NiO is added to the anode sample. The effect of NiO content on the microstructures, surface area, and electric conductivity of these Ni-BSCZY (NiO55-BSCZY, NiO60-BSCZY, and NiO65-BSCZY) anode materials were systematically investigated using X-ray diffraction, scanning electron microscopy, an analytic technique based on the Brunauer–Emmett–Teller surface area theory, and four-probe conductivity analysis. In addition, three anode-supported cells containing identical electrolytes but various combinations of NiO and BSCZY anode materials were fabricated and used for performance and electrochemical impedance measurement. The results revealed that the reactive surface area of the anode in contact with the electrolyte plays a crucial role in total cell performance. The cell containing the anode material (NiO60-BSCZY) with the highest surface area of 6.91 m² g⁻¹ and the lowest total resistance of 2.19 Ω cm² exhibited the highest power density of 169.2 mW cm⁻² at 800 °C.     

Enhanced sintering of Ce0.8Nd0.2O2−δ-La0.8Sr0.2Ga0.8Mg0.2O3−δ using CoO as a sintering aid

Ce_0.8Nd_0.2O_1.9 (NDC) and La_0.8Sr_0.2Ga_0.8Mg_0.2O_3-δ (LSGM) electrolytes were prepared using a sol-gel method. NDC-LSGM composite electrolytes were subsequently prepared by adding 5% (w, mass fraction) precalcined LSGM powders to NDC sols. The electrolyte materials of NDC-Co and NDC-LSGM-Co were obtained by adding 1 mol% CoO to NDC sols and NDC-LSGM composite electrolytes, respectively. The microstructure and phase composition of the pellets were characterized using X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), and energy dispersive X-ray spectroscopy (EDS). The electrical conductivities of the pellets were measured using alternative current (AC) impedance spectroscopy. The results indicate that a single perovskite phase is observed for the LSGM ceramic, while NDC-Co, NDC-LSGM and NDC-LSGM-Co have a cubic fluorite structure similar to that of NDC. As a sintering aid, CoO can further promote grain growth and increase relative density (＞95%) of the NDC-LSGM composite electrolyte. The enhancement of the total conductivity is primarily attributed to the large increase in the conductivity of the grain boundary. However, the slight decrease of the grain boundary conductivity of the NDC-LSGM-Co electrolyte is caused by the presence of trace amounts of impurity phases in the grain boundaries.     

高熵稳定双钙钛矿阴极材料SmBa(Mn0.2Fe0.2Co0.2Ni0.2Cu0.2)2O5+δ的制备及性能优化

通过改进的自蔓延燃烧法合成制备高熵双钙钛矿SmBa(Mn0.2Fe0.2Co0.2Ni0.2Cu0.2)2O5+δ(HE-SBC)阴极材料,并复合10％(摩尔分数)Gd2O3掺杂CeO2(GDC)以优化性能.结果表明:通过B位高熵的方法可以显著减小Co离子由价态变化而引起的热膨胀,从而降低SmBaCo2O5+δ的热膨胀...     

Ablation behavior of high-entropy carbides ceramics (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C upon exposition to an oxyacetylene torch at 2000 °C

The ablation performance of a high-entropy ceramic carbide, (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C, was performed by oxyacetylene ablation flame, simulating the extreme service environment at 2000 ºC. Phase and microstructure characterization at multi-length scales was carried out. During ablation, a compositionally and microstructurally complex oxidation layer formed on the ablation surface, which consisted of a combination of (Zr_xHf_1?x)₆(Nb_yTa_1?y)₂O₁₇, Ti(Nb_xTa_1?x)₂O₇, and Ti_x(Zr_aHf_bNb_cTa_1?a-b-c)_1?xO₂. Based on the microstructure information, the ablation mechanisms were proposed considering the oxidation thermodynamics and kinetics. Comparable rates of O inward diffusion and Ti outward diffusion are suggested, and a particular innermost dense layer composed of isolated (Zr_xHf_1?x)₆(Nb_yTa_1?y)₂O₁₇ grains embedded in a continuous Ti(Nb_xTa_1?x)₂O₇ matrix is considered to be beneficial for a better ablation resistance.     

A new type of Sr(Zr0.2Hf0.2Ce0.2Yb0.2Me0.2)O3−x (Me = Y,Gd) high-entropy ceramics used in thermal barrier coatings

Seeking for new ceramics with excellent thermophysical properties as thermal barrier coatings candidate materials has become a hot research field. In this study, Sr(Zr_0.2Hf_0.2Ce_0.2Yb_0.2Me_0.2)O_3−x high-entropy ceramic powders were successfully synthesized by the method of solid-state reaction, and the ceramics with single phase were prepared by pressureless sintering at 1600°C. The phase composition, microstructure, element distribution, high-temperature thermal stability, and thermophysical properties of the ceramics were studied. The results showed that Sr(Zr_0.2Hf_0.2Ce_0.2Yb_0.2Me_0.2)O_3−x ceramics were composed of SrZrO₃ phase and the second phase of AB₂O₄ spinel (i.e., SrY₂O₄ and SrGd₂O₄). The content of the second phase was gradually increased after heat treatment at 1400°C, which significantly improved the thermophysical and mechanical properties of the ceramics. The microhardness and fracture toughness of the ceramics were improved compared with that of SrZrO₃. The thermal conductivities of Sr(Zr_0.2Hf_0.2Ce_0.2Yb_0.2Me_0.2)O_3−x (Me = Y, Gd) ceramics were 1.30 and 1.28 W m⁻¹ K⁻¹ at 1000°C, which were about 35% and 40% lower than that of SrZrO₃ (1.96 W m⁻¹ K⁻¹) and yttria-stabilized zirconia (2.12 W m⁻¹ K⁻¹), respectively. The thermal expansion coefficients of Sr(Zr_0.2Hf_0.2Ce_0.2Yb_0.2Me_0.2)O_3−x (Me = Y, Gd) ceramics were 12.8 × 10⁻⁶ and 14.1 × 10⁻⁶ K⁻¹ at 1300°C, respectively, which was more closer to the superalloys compared with SrZrO₃ ceramic (11.0 × 10⁻⁶ K⁻¹).     

Influence of component manipulation on the structural,mechanical, thermophysical and electrical properties of La0·2Ce0.2Nd0.2(ZrxY1−x)0.4O2−δ high-entropy ceramics

A series of high-entropy ceramics (HECs) with compositions of La_0·2Ce_0.2Nd_0.2(Zr_xY_1−x)_0.4O_2−δ (x = 0.5, 0.6, 0.7, 0.8, 0.9 and 1.0, the corresponding names being HEC(Zr_0·5/Y_0.5, Zr_0·6/Y_0.4, Zr_0·7/Y_0.3, Zr_0·8/Y_0.2, Zr_0·9/Y_0.1, Zr_1·0/Y₀)) were sintered in air at 1600 ^°C for 10 h. When x is in the range of 0.5–0.7, a fluorite phase is formed. Then, as x exceeds 0.7, a second pyrochlore-structured phase appears, and its content gradually increases with the increasing x. The grain growth of the samples is inhibited by increasing in the relative Zr content. The grain refinement and the formation of second phase reduce the thermal conductivity and reinforce the mechanical properties of the samples. HEC(Zr_0.9/Y_0.1) has the lowest thermal conductivity (50–500 °C) and brittleness index, as well as the highest fracture toughness among all samples. In addition, La_0·2Ce_0.2Nd_0.2(Zr_xY_1−x)_0.4O_2−δ ceramics have excellent thermal stability under Ar atmosphere in 50–1400 °C. The thermal expansion coefficients of the samples marginally change regardless of the variation in x. All samples show higher oxygen barrier property than Y₂O₃-stabilized ZrO₂.     

(La0.2Sm0.2Nd0.2Y0.2Er0.2)2Zr2O7高熵陶瓷结构及热物理性能研究

采用固相法合成(La_0.2Sm_0.2Nd_0.2Y_0.2Er_0.2)₂Zr₂O₇陶瓷材料,并使用XRD、SEM、热膨胀仪和激光导热仪对其物相、形貌、热膨胀性能和热导率进行测试和分析。结果表明：(La_0.2Sm_0.2Nd_0.2Y_0.2Er_0.2)₂Zr₂O₇陶瓷材料表现为单一的烧绿石结构,晶粒致密,晶界清晰且有较高的致密度,平均热膨胀系数为1.138×10^-5 K^-1,1 000℃时热导率为2.14 W·m^-1·K^-1。     

单晶型和团聚型LiNi0.6Co0.2Mn0.2O2正极材料性能对比

采用固相合成工艺,对制备出的单晶Li Ni0. 6Co0. 2Mn0. 2O2(S-NCM622)和团聚型Li Ni0. 6Co0. 2Mn0. 2O2(P-NCM622)材料进行物化指标和电性能指标对比。通过激光粒度仪、X射线衍射(XRD)、扫描电镜(SEM)、差热分析DSC等测试分析表明,D50为4. 0μm的SNCM622材料粉末压实密度为3. 4g/cm3,D50为10μm S-NCM622材料粉末压实密度为3. 2 g/cm3。S-NCM622材料3. 0-4. 4 V下扣式电池0. 1C放电容量为190. 5mAh/g,比P-NCM622材料低0. 7mAh/g; 3. 0-4. 4V 45°C下1C充放80周,循环保持率为98%,比PNCM622材料高5%。将两者制作成600mAh的小软包电池,在3. 0-4. 3 V下,60°C放置30天后测试,S-NCM622材料鼓胀率为8. 7%,P-NCM622材料鼓胀率为12. 3%,前者容量恢复率为94. 9%,后者仅为89. 2%。4. 3V下扣电测试DSC,S-NCM622和PNCM622放热峰温度和放热起始点温度分别为284. 1°C、279. 6°C和286. 8°C、283. 5°C。     

Direct oxidation of dry methane on nanocrystalline Ce0.8Gd0.2O2-δ/Pt anodes

The electrocatalytic activity of composite anodes, consisting of micron-scale sized Pt particles and nanocrystalline Ce_0.8Gd_0.2O_2-δ(CGO) prepared by the cellulose-precursor technique, was evaluated for the oxidation of dry methane in a solid oxide fuel cell (SOFC) with zirconia-based electrolyte at 1173 K. Increasing current density above 100 mA/cm² and the corresponding decrease of CH₄/O₂ ratio down to 2–3 suppressed carbon formation, but decreased CO/CO₂ molar ratio in the product mixture to 0.3–0.9. The methane conversion rate was found to increase linearly with current, suggesting an increasing role of total CH₄ oxidation by oxygen electrochemically supplied onto the anode surface. The results show that, although ceria-based anode components are well known to improve SOFC performance, their presence leads to high CO₂ selectivity and thus seems inappropriate for the generation of synthesis gas in SOFC-type reactors.     

(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)Fe2O4高熵陶瓷的制备与吸波性能

采用固相反应法制备了单相块体(Mg_0.2Co_0.2Ni_0.2Cu_0.2Zn_0.2)Fe₂O₄高熵尖晶石陶瓷。结合X射线衍射，扫描电子显微镜和能谱仪对制备过程中的物相组成、显微结构和元素分布进行分析。随烧结温度的升高陶瓷材料体积密度增大，气孔率降低，1 200℃烧结所得致密高熵尖晶石陶瓷材料呈单相，元素均匀分布，其弯曲强度和断裂韧性分别达43.00 MPa和1.30 MPa·m^1/2。所制备高熵尖晶石陶瓷对电磁波兼具介电损耗和磁损耗能力，其在3.0 mm处可获得最大的有效吸收带宽为12.37 GHz，是具有一定承载能力和优异宽频吸波性能的陶瓷材料。     

锂离子电池LiNi0.6Co0.2Mn0.2O2正极材料的硼元素掺杂改性调控

采用草酸盐共沉淀法结合后续热处理技术制备硼掺杂LiNi0.6Co0.2Mn0.2O2正极材料.研究了不同硼源(B2O3,H3BO3和LiBO2)掺杂对材料形貌、结构和电化学性能的影响.通过X射线衍射仪和Rietveld精修分析证明了硼(B)元素掺杂到材料晶格中.电化学性能研究表明:B2O3掺杂效果最佳,具有优异的倍率性...     

ZrO_2包覆富锂正极材料Li[Li_(0.2)Ni_(0.2)Mn_(0.6)]O_2

采用共沉淀-高温固相法制备了富锂正极材料Li[Li0.2Ni0.2Mn0.6]O2,并使用Zr(OC3H7)4进行了Zr O2包覆改性。通过X射线粉末衍射(XRD)、透射电子显微镜(TEM)和电化学测试手段讨论了Zr O2包覆对材料的结构、形貌和电化学性能的影响。Zr O2能均匀覆盖在Li[Li0.2Ni0.2Mn0.6]O2颗粒表面,包覆后材料的电化学性能有一定的改善。包覆质量分数0.5%的Zr O2样品表现了提高的循环和倍率性能。首次放电容量(0.1 C,2.0~4.8 V)高达250.8 m Ah·g-1,循环45周(0.2C)容量保持为201.6 m Ah·g-1,2.0 C倍率放电容量可达123.2 m Ah·g-1。     

Spray-dry synthesis of β-Cu1.8Zn0.2V2O7 ceramic fine particles showing giant negative thermal expansion

We used spray-dry method to synthesize fine powder of β-Cu_1.8Zn_0.2V₂O₇ showing large negative thermal expansion (NTE) linearly to temperature over a wide temperature range. The NTE of β-Cu_1.8Zn_0.2V₂O₇ is produced by microstructures consisting of voids and anisotropic thermal deformation of crystal grains in ceramics. By reducing the size of the microstructures that produce NTE, large NTE equivalent to that of bulk was realized, even for ceramic particles of about 2 μm size. Comparison with particles produced using a conventional method demonstrates that the particle size distribution is narrow and that the particles are nearly spherical. This achievement is expected to pave the way to use of NTE materials in micrometer-scale control of thermal expansion.     

锂离子电池正极材料LiNi0.8M0.2O2的制备

在增加氧气压力的条件下，采用固相反应制得一系列掺杂不同元素M的锂离子电池正极材料LiNi0.8M0.2O2. 研究发现，掺杂Al, Mn, Ti可以改善材料的耐过充性和循环性能，在充电电压为4.2~4.8 V的范围内循环3次，材料的放电容量没有显著的改变. X射线衍射和扫描电镜分析表明，掺杂Al, Mn, Ti提高了镍酸锂材料的六方菱型结构的有序性，维持了在充放电过程中的层状结构的稳定性. 其它掺杂元素降低了材料结构的有序性，影响了其电化学性能. 说明形成完整的晶体结构是掺杂元素的选择依据.     

Effect of heat treatment on the anodic oxidation of Ti–0.2 Pd alloys in chloride solutions

The effect of heat treatment of Ti and Ti–0.2 Pd alloys on their anodic oxidation was studied in deaerated 1% NaCl by means of anodic linear sweep voltammetry, SEM, TEM, EDS, optical microscopy and microhardness measurements. The specimens, as fabricated, consisted of -phase only. The -phase, intergranular or with a Widmansttäten type growth, was produced by heat treatment of the Ti–0.2 Pd alloys at the temperature range from 750 to 850 C. The -phase was transformed into the -phase during quenching. The current density against voltage curves for pure Ti and Ti–0.2 Pd, as fabricated or heat-treated, presented an initial plateau at about 1.5 V vs Ag/AgCl/KCl (3 M), an anodic peak at about 4.5 V and a current increase due to the pitting attack at about 10 V. The anodic peak was related to an oxide growth together with a solution electrolysis. Current spikes appeared at random from potentials about 8.3 V, which were related to film breakdown and repair events. The passive films of the alloys oxidized up to about 10 V presented oxidation bands parallel to the surface, with different oxygen content and microhardness, together with a structural transformation of the -phase under the titanium oxide layer. The similar behaviour of pure Ti and Ti–0.2 Pd alloys in front of pitting corrosion in chloride was due to such a structural transformation.     

高密度LiNi_(0.8)Co_(0.2)O_2的合成

以二次干燥化学共沉淀法制得高密度前驱体Ni0.8Co0.2(OH)2,再与LiNO3混合,经600℃恒温6 h,800℃恒温24 h两个恒温阶段烧结,得到高密度LiNi0.8Co0.2O2,探讨了锂源、镍源、Li/(Ni+Co)摩尔比、合成温度等因素对产品的影响,优化了LiNi0.8Co0.2O2的合成工艺。所得非球形LiNi0.8Co0.2O2粉末振实密度高达3.15 g/cm3,大幅度地提高正极材料的体积比能量。X射线衍射分析表明,合成的LiNi0.8Co0.2O2具有规整的层状NaFeO2结构,充放电测试表明,材料具有良好的电化学性能。     

湿法包覆LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2合成、结构与性能的研究

采用共沉淀-固相烧结-湿法包覆方法制得一系列622三元材料,通过SEM、XRD(原位和Retvield法精修)以及电化学测试,对纯相材料和不同热处理温度包覆修饰材料的形貌、结构、电化学性能进行了表征。结果表明经包覆处理后,与纯相材料相比较,包覆后的材料结构稳定、电化学性能优良。