高镍正极材料LiNi0.6Co0.2Mn0.2O2的研究进展

高镍正极材料LiNi_0.6Co_0.2Mn_0.2O₂(NCM622)由于比容量高、价格低等优点,被认为是最有前景的正极材料之一。在介绍NCM622存在的问题的基础上,分别从合成方法、改进措施等方面进行总结,并对NCM622的未来发展进行展望。     

Si衬底上La0.8Sr0.2MnO3/SrMnO3双层结构研究

利用磁控溅射方法在Si(100)衬底上首先生长SrMnO3(SMO)作为缓冲层,再沉积La0.8Sr0.2MnO3(LSMO)薄膜,得到(110)面择优生长的LSMO/SMO双层结构.利用X射线衍射仪分析了SMO缓冲层的结构特征对LSMO薄膜择优取向生长的影响;利用Rutherford背散射(RBS)分析了LSMO/SMO间的界面情况.结果表明以SMO作为单一缓冲层时,不仅可以实现LSMO薄膜在Si(100)衬底上的(110)面的择优生长,而且LSMO/SMO的界面扩散现象也不明显.     

Synthesis and properties of Ba0.5Sr0.5(Co0.6Zr0.2)Fe0.2O3−δ perovskite cathode material for intermediate temperature solid-oxide fuel cells

A highly stable perovskite cathode material, Ba_0.5Sr_0.5(Co_0.6Zr_0.2)Fe_0.2O_3−δ (BSCZF) for intermediate temperature solid-oxide fuel cells (IT-SOFCs) was synthesized via the improved EDTA-citric acid complexing technique combined with high-temperature sintering. The product was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical impedance spectra (EIS) measurements. An electrolyte-supported BSCZF/SDC/Ni-SDC fuel cell was fabricated to evaluate the performance of the material. The XRD study indicates that the sintering temperature higher than 950 °C is sufficient to the formation of clean single BSCZF perovskite phase. Due to the incorporation of Zr ions, BSCZF perovskite exhibit lower electrical conductivity with higher activation energy but higher structural stability than the Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) parent oxide. The maximum electrical conductivity of BSCZF attains 16.9 S cm⁻¹ at around 540 °C. Impedance spectra showed that the ASRs of BSCZF cathode on samaria doped ceria (Ce_0.8Sm_0.2O_1.9, SDC) electrolyte are low but are still slightly larger than those of BSCF at similar conditions. The BSCZF/SDC/Ni-SDC cell exhibited a stable output with the maximum power densities of 30, 75, 139 and 241 mW cm⁻² at 550, 600, 650 and 700 °C, respectively. Due to the high electrochemical performances as well as the excellent stability, BSCZF perovskite may be an attractive cathode material for IT-SOFCs.     

Er2O3掺杂Gd2(Zr0.8Ti0.2)2O7陶瓷的物理性能

用固相反应法制备(Gd_1-xEr_x)₂(Zr_0.8Ti_0.2)₂O₇(摩尔分数x=0,0.2,0.4)陶瓷并测试其晶体结构、显微形貌和物理性能,研究了Er₂O₃掺杂的影响。结果表明,(Gd_1-xEr_x)₂(Zr_0.8Ti_0.2)₂O₇陶瓷具有立方烧绿石结构,显微结构致密,在室温至1200℃高温相的稳定性良好;Er³⁺掺杂降低了陶瓷材料的热导率和平均热膨胀系数,当x=0.2时,其1000℃的热导率最低(为1.26 W·m^-1·k^-1)。同时,Er³⁺掺杂还提高了这种材料的硬度和断裂韧性。     

Effect of piezoelectric grain size on magnetoelectric coefficient of Pb(Zr0.52Ti0.48)O3–Ni0.8Zn0.2Fe2O4 particulate composites

This study investigates the variation of magnetoelectric (ME) coefficient as a function of the piezoelectric grain size in the composite system of 0.8 Pb(Zr_0.52Ti_0.48)O₃–0.2 Ni_0.8Zn_0.2Fe₂O₄. It was found that as the piezoelectric-phase grain size increases the overall resistivity, piezoelectric, dielectric, and ferroelectric property of the composite increases and saturates above 600 nm. Below 200 nm average grain size, piezoelectric and dielectric properties decrease rapidly. The ferroelectric Curie temperature was found to decrease from 377 to 356 °C as the average grain size decreases from 830 to 111 nm. ME coefficient of the composite showed a rapid change below grain size of 200 nm and was found to saturate above 600 nm to a value of 155 mV/cm.Oe.     

Nanoparticles of La0.8Ca0.2Fe0.8Ni0.2O3−δ perovskite for solid oxide fuel cell application

Polycrystalline samples of La_0.8Ca_0.2Fe_0.8Ni_0.2O_3−δ (LCFN) with perovskite type structure have been prepared by combustion, freeze drying, citrate-gel process and liquid mix method. The analysis of X-ray powder diffraction indicated that the samples were single phase and crystallized in an orthorhombic (space group, Pnma no. 62) structure.Transmission electron microscopy (TEM) analysis on the synthesized powder at 600 °C by liquid mix method showed clusters of 150 nm formed by nanoparticles of 20 nm. Electrochemical performance of LCFN cathodes, which are used for intermediate temperature solid oxide fuel cells, were investigated. The polarization resistance was studied using two different electrolytes: Y-doped zirconia (YSZ) and Sm-doped ceria (SDC). The dc four-probe measurement exhibits a total electrical conductivity, over 100 S cm⁻¹ at T ≥ 600 °C, pointing out that strontium can be substituted for the cheaper calcium cation without destroying the electrochemical properties. Experimental results indicate that nanoparticles have more advantages in terms of smaller particle size and better electrochemical performance.     

Synthesis and Superconductivity of New Cuprates (Pb0.8W0.2)Sr2(Nd1 ? xCax)Cu2O7 ? δ

New cuprates with nominal composition (Pb_0.8W_0.2)Sr₂(Nd_{1 – x} Ca _x )Cu₂O_{7 –} (0x1) were synthesized by solid-state reaction in N₂. The crystal structure was characterized by X-ray powder diffraction (XRD) as tetragonal. Direct current electrical resistance measurements were applied to check the existence of superconductivity in these cuprates. Superconductivity with T _c (onset) up to 82 K is observed when x = 0.6. Synthesis in N₂ is necessary in obtaining superconductivity in these cuprates. Preparation in air or post-treatment in flowing oxygen destroys superconductivity. A comparison is made with previous Pb-based 1212 superconducting oxides. The valence of Pb and the possible position of W in the lattice are discussed.     

La0.8Sr0.2CoO3的拉曼光谱特性研究

采用柠檬酸盐法制备了斜方六面体型(rhombohedral)钙钛矿材料La0.8Sr0.2CoO3,测量了它的拉曼光谱,我们发现随着测量用激光的激发功率的增加,705cm-1附近的拉曼振动峰不断移动,且拉曼峰的强度也不随激发功率的增加而线性增加,当激发功率达到1.5mW时,材料出现荧光,随激发光增强,荧光快速增大,同时拉曼峰消失.     

Indentation strength method to determine the fracture toughness of La0.58Sr0.4Co0.2Fe0.8O3-δ and Ba0.5Sr0.5Co0.8Fe0.2O3-δ

The temperature-dependent fracture toughness of brittle ceramics can be conveniently assessed from bending tests of specimens with defined cracks introduced by indentation. However, the validity of this indentation strength in bending method (ISM) depends critically on the correct consideration of the residual stress induced by the indentation process. The ISM has been applied to La_0.58Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) and, for comparison, on Ba_0.5Sr_0.5Co_0.2Fe_0.8O_3-δ (BSCF) perovskite. LSCF with rhombohedral phase exhibits ferro-elastic behavior at ambient temperature, whereas BSCF deforms linear-elastically. Pre-indented specimens of both perovskites were fractured at room temperature in biaxial bending, some of them after an additional annealing step. The fracture toughness values of BSCF match reasonably well when determined with equations which consider the presence or absence of residual indentation stress. Interestingly, annealing has little influence on the apparent toughness results obtained for rhombohedral LSCF, which appears to be related with stress relaxation by ferro-elastic deformation.     

Electrical resistivity of the hole doped La0.8Sr0.2MnO3 manganites: Role of electron–electron/phonon/magnon interactions

In this work, a quantitative analysis of reported metallic and insulating behaviour of resistivity in perovskite manganites La_0.8Sr_0.2MnO₃ is established. An effective inter-ionic interaction potential (EIoIP) with the long-range Coulomb, van der Waals (vdW) interaction and short-range repulsive interaction up to second-neighbour ions within the Hafemeister and Flygare approach was employed to estimate the Debye and Einstein temperature and was found to be consistent with the available experimental data. The electrical resistivity data in low temperature regime (T < T_MI) were theoretically analyzed within the framework of the classical electron–phonon model of resistivity, for example, the Bloch–Gruneisen (BG) model. The Bloch–Gruneisen (BG) model and terms T², T^4.5 simplify the electron–phonon, electron–electron and electron–magnon scattering processes. On the other hand, in high temperature regime (T > T_MI) the insulating nature is discussed with Mott's variable range hopping (VRH) model and small polaron conduction (SPC) model. For T > T_MI SPC model is more appropriate than the VRH model. The SPC model consistently retraces the higher temperature resistivity behaviour (T > θ_D/2). The metallic and semiconducting resistivity behaviours of La_0.8Sr_0.2MnO₃ manganites are analyzed, to the knowledge, for the first time highlighting the importance of electron–phonon, electron–electron, electron–magnon interactions and small polaron conduction.     

Sm2O3掺杂(Ba0.7Ca0.3)TiO3-Ba(Zr0.2Ti0.8)O3无铅压电陶瓷的制备与性能

采用固相合成法制备了Sm2O3掺杂的(Ba0.7Ca0.3)TiO3-Ba(Zr0.2Ti0.8)O3(BCZT)无铅压电陶瓷.借助XRD、SEM等手段对该陶瓷的显微结构与电性能进行了研究.结果表明,Sm2O3的掺杂降低了BCZT无铅压电陶瓷的烧结温度并使居里温度点Tc从85℃提高到95℃.当Sm2O3掺杂量为0.02wt%～0.1wt%时,样品具有典型ABO3型钙钛矿结构.Sm2O3掺杂量为0.02wt%时,所得陶瓷样品具有最优综合电性能,其压电常数d33、机电耦合系数kp、机械品质因子Qm、介电损耗tanδ和介电常数εr分别为590 pC/N、0.52、43、1.3%和3372.     

Processing and magneto-electric properties of sol–gel-derived Pb(Zr0.52Ti0.48)O3–Ni0.8Zn0.2Fe2O4 2-2 type multilayered films

Pb(Zr_0.52Ti_0.48)O₃–Ni_0.8Zn_0.2Fe₂O₄ (PZT–NZFO) multilayered thin films with various volume fractions of the PZT phase (100, 74, 58, 48, 33, and 0%) were prepared on Pt/Ti/SiO₂/Si substrates using sol–gel spin-coating method. X-ray diffraction shows polycrystalline structure and scanning electron microscopy reveals good multilayer morphology of the composite thin film as annealed at 700 °C in air. The thickness of the composite films was estimated in the range of ~400 to ~600 nm. The ferroelectric and magnetic properties were measured as function of the volume fractions of the PZT phase. The magnetoelectric (ME) effect was investigated under various bias magnetic fields. The maximum ME voltage coefficient (α _E  = dE/dH) is 278 mV/cmOe for the composite film with the volume fractions of the PZT phase of ~48%.     

Gd0.2Ce0.8O2包覆LaNi0.6Fe0.4O3-δ阴极材料抗铬污染性能

应用丝网印刷和共烧结制备LaNi_0.6Fe_0.4O_3-δ (LNF)/Sc_0.1Zr_0.9O_1.95(ScSZ)/LaNi_0.6Fe_0.4O_3-δ 对称电池.以硝酸铈和硝酸钆为原料、柠檬酸为燃料,采用燃烧法制备质量分数为21.3%的Gd_0.2Ce_0.8O₂(GDC)包覆的LNF阴极.电化学阻抗谱(EIS)表明:在750 ℃工作温度下,当无Cr基合金接触时,质量分数21.3%的GDC包覆的LNF经过1 200 h的搁置,其极化电阻由0.13 Ω·cm²增加至0.40 Ω·cm²,而纯LNF经过500 h的搁置,极化电阻由0.70 Ω·cm²增加至2.36 Ω·cm²,GDC的包覆加速了气体/阴极/电解质三相界面反应区的扩散过程,降低了阴极极化电阻;当有Cr基合金接触时,相对于质量分数为21.3%的GDC包覆的LNF阴极,LNF/ScSZ界面处沉积出大量Cr₂O₃,减缓了活性粒子在三相界面处的扩散,故其极化电阻远大于相同条件下质量分数为21.3%的GDC包覆的LNF阴极的极化电阻,质量分数为21.3%的GDC包覆的LNF阴极具有较佳的抗铬污染性能.     

Phase composition and structure of La1 ? x Ca x MnO3 + δ (0 ≤ x ≤ 0.2) solid solutions

A structural phase diagram of La_{1 − x} Ca _x MnO_{3 + δ} (0 ≤ x ≤ 0.2) solid solution in air has been constructed for the first time, and the equilibrium T-x fields of the monoclinic, orthorhombic, and rhombohedral phases in this system have been outlined. The transitions between these phases are accompanied by sharp changes in lattice parameters, suggesting that they are first-order. Original Russian Text ? S.Kh. Estemirova, A.M. Yankin, S.G. Titova, V.F. Balakirev, Yu.E. Turkhan, 2008, published in Neorganicheskie Materialy, 2008, Vol. 44, No. 11, pp. 1387–1392.     

BaCo0.2Fe0.6Ti0.2O3-δ的制备、氧非化学计量和电子输运性能研究

采用修饰的Pechini方法制备了纯相BaCo0.2Fe0.6Ti0.2O3-δ(BCFT)样品.X射线衍射(XRD)证明了该方法制备的陶瓷粉体及烧结样品为单一的六方钙钛矿相结构.扫描电镜(SEM)观察显示BCFT烧结样品具有均匀的微结构.电导测量显示在570℃以下具有电阻负温度系数(NTC)特征,而在570～1000℃则呈电阻正温度系数(PTC)特征,结合碘滴定对BCFT样品在不同温度下的氧非化学计量测量结果,分析认为该电导出现极值的现象是因为高温晶格氧析出导致样品空穴载流子浓度降低所致.对电阻负温度系数温度段的电子输运性能和稳定性的研究表明,BCFT在200～300℃之间具有较好的阻温特征和重复性,有望作为一种在该温度段使用的新型NTC材料.     

Investigation on preparation of nano-size Gd0.2Ce0.8O2?δ material and its humidity sensing properties

The mixed-conductive ceramic oxide Gd_0.2Ce_0.8O_2−δ (GCO) particles with 40–50 nm were synthesized by using a combined citrate and EDTA complexation method. The material was characterized with powder X-ray diffraction, transmission electron microscopy, energy dispersive spectrometry, and X-ray photoelectron spectroscopy. A humidity sensor was fabricated by screening GCO onto a ceramic substrate with a pair of interdigitated electrodes. The sensor shows a linear relationship between logarithm impedance and relative humidity in the range of 33–98% when the measurement frequency range is 20 Hz–1 kHz. Typical response and recovery times of the sensor are 40 and 210 s, respectively, indicating that desorption rate of water molecule inside the GCO material is slower than the adsorption rate. The humidity sensing mechanism was discussed.     

烧结助剂CuO对Ce0.8Gd0.2O1.9性能影响的研究

采用传统的固相反应法制备了CGO(Ce0.8Gd0.2O1.9)固体电解质,研究了CuO烧结助剂对CGO的体密度、相组成、微观结构及电性能的影响。结果表明,加入CuO的样品的体密度随烧结温度的升高而增大,1300℃烧结的样品致密化程度最高,当烧结温度为1350℃时,样品有过烧现象。与纯的CGO相比,CuO的加入使样品的烧结温度降低了将近300℃,而且经高温烧结后仍为立方萤石结构,无新相生成。CGO交流阻抗谱与电导率分析表明,当CuO的掺杂量为1%(摩尔分数),烧结温度为1300℃时电导率最高,所以CuO作为烧结助剂不仅降低了烧结温度,使晶粒尺寸减小,同时还提高了电导率,因而CuO是很好的烧结助剂。     

La0.5Y0.5Ni4.8Mn0.1Al0.1和La0.5Y0.5Ni4.8Al0.2合金的储氢性能研究

针对两种新型稀土型储氢合金La0.5Y0.5Ni4.8Mn0.1Al0.1和La0.5Y0.5Ni4.8Al0.2的储氢特性进行研究分析。实验表明,相同温度下,La0.5Y0.5Ni4.8Mn0.1Al0.1和La0.5Y0.5Ni4.8Al0.2合金的PCT曲线基本重合,且都具有优良的吸氢动力学性能;相比之下,后者的滞后系数要小于前者,吸氢量较大,吸氢速率也较快,故其储氢性能较优。300次吸放氢循环实验结果表明,La0.5Y0.5Ni4.8Al0.2合金的吸氢动力学性能虽然略有下降,但抗粉化性能较好。     

Synthesis and properties of magnetic solid superacid: SO4/ZrO2–B2O3–Fe3O4

A magnetic SO₄²⁻/ZrO₂–B₂O₃–Fe₃O₄ solid superacid catalyst is prepared via a simple chemical co-precipitation approach. The obtained materials were characterized in detailed by X-ray powder diffraction, thermogravimetric analysis–different scanning calorimetry, Fourier transform infrared spectroscopy (FTIR), electron microscopy (SEM and TEM), and Mossbauer spectra. Powder X-ray diffraction patterns show that in this composite oxide the transformation temperature of ZrO₂ from tetragonal to monoclinic phase is higher compared to the pristine SO₄²⁻/ZrO₂ material. The introduction of Fe₃O₄ endows the superacid with a super-paramagnetic property while in a ferromagnetic state after calcination. The superacid exhibits high catalytic activity in forming ethyl acetate by esterification.