Bandgap narrowing in the layered oxysulfide semiconductor Ba_3Fe_2O_5Cu_2S_2: Role of FeO_2 layer

A new layered Cu-based oxychalcogenide Ba_3Fe_2O_5Cu_2S_2 has been synthesized and its magnetic and electronic properties were revealed. Ba_3Fe_2O_5Cu_2S_2 is built up by alternatively stacking [Cu_2S_2]~(2-) layers and iron perovskite oxide[(FeO_2)(BaO)(FeO_2)]~(2-)layers along the c axis that are separated by barium ions with Fe~(3+) fivefold coordinated by a square-pyramidal arrangement of oxygen. From the bond valence arguments, we inferred that in layered CuC h-based(Ch =S, Se, Te) compounds the +3 cation in perovskite oxide sheet prefers a square pyramidal site, while the lower valence cation prefers the square planar sites. The studies on susceptibility, transport, and optical reflectivity indicate that Ba_3Fe_2O_5Cu_2S_2 is an antiferromagnetic semiconductor with a Ne′el temperature of 121 K and an optical bandgap of 1.03 eV. The measurement of heat capacity from 10 K to room temperature shows no anomaly at 121 K. The Debye temperature is determined to be 113 K. Theoretical calculations indicate that the conduction band minimum is predominantly contributed by O 2p and 3 d states of Fe ions that antiferromagnetically arranged in FeO_2 layers. The Fe 3d states are located at lower energy and result in a narrow bandgap in comparison with that of the isostructural Sr_3Sc_2O_5Cu_2S_2.     

室温钠离子电池材料及器件研究进展

在众多电化学储能技术中,室温钠离子电池除具有能量密度高、循环寿命长的特点外,还具有其他电池体系所不具有的资源丰富和成本低廉的优势,是一种较理想的规模储能电池体系.中国科学院物理研究所自2011年以来致力于低成本、安全环保的钠离子电池技术的研发,在正、负极材料和电解质材料开发中取得了多项原创性的研究成果,并研制出Ah级钠离子软包电池.例如,首次发现Cu~(2+)/Cu~(3+)氧化还原电对高度可逆并设计了Na-Cu-Fe-Mn-O基低成本层状氧化物正极材料;首次通过简单的一步碳化法制备出性价比高的无烟煤基负极材料;首次将一种新型的钠盐NaFSI应用于碳酸酯非水电解质以大幅度提升电极材料的性能等.本文综述了物理所在钠离子电池材料及器件研究中所取得的重要进展和突破,期待经过进一步不懈地努力为实现钠离子电池的产业化做出重要贡献.     

Relationship between electronic and crystal structure in Cu–Ni–Co–Mn–O spinels: Part A: Temperature-induced structural transformation

Local atomic and crystal structures around Cu and Mn atoms in Mn_1.68Cu_0.6Ni_0.48Co_0.24O₄ spinel samples fabricated by metal–organic decomposition synthesis at different annealing temperatures were investigated by X-ray absorption fine structure analysis. There are two distinct copper cations, Cu¹⁺ and Cu²⁺, both of which maintain tetrahedral coordination. The bond-length distances are Cu¹⁺–O = 2.00 Å and Cu²⁺–O = 1.80 Å. The manganese cations are for the most part octahedral. The spinels prepared at low temperature (600 °C) contain smaller (Mn⁴⁺–O = 1.88 Å) undistorted MnO₆ octahedrons corresponding to Mn⁴⁺ valence, whereas the manganese octahedrons in high-temperature materials (800 °C and higher) were larger and had a pronounced tetragonal distortion pertaining to Mn³⁺ oxidation state (Mn³⁺–O = 1.93 Å and 2.11 Å). By rising the fabrication temperatures, relative concentration of the species of Mn⁴⁺ and Mn³⁺ varies as a result of the reaction represented by Cu¹⁺ + Mn⁴⁺  Cu²⁺ + Mn³⁺, implying irreversible temperature-induced structural transformation. Atomic coordinates in the low-temperature phase are similar to those found in the ideal cubic spinel with oxygen parameter u = 0.27, whereas local environments of the Cu and Mn atom correspond to the tetragonal CuMn₂O₄ phase (space group I4₁/amd). Unlike in CuMn₂O₄, orientation of the lattice distortions is random, however, the long-range cubic spinel structure is retained at all time.     

Relationship between electronic and crystal structure in Cu–Ni–Co–Mn–O spinels: Part B: Binding energy anomaly in Cu photoemission spectrum

In very rare circumstances, X-ray photoemission spectra of copper in spinel oxides exhibit a “negative binding energy shift”. The origin of such an anomalous XPS chemical shift was investigated. A metastable Ni_0.48Co_0.24Cu_0.6+xMn_1.68−xO₄ (0 < x < 0.6) spinel was fabricated at 600 °C using a low-temperature solution technique. The binding energy of the 2p_3/2 level of copper (930.8 eV) is found 1.9 eV lower than that of Cu⁰ (932.7 eV). XPS and EXAFS studies revealed that the post-thermal annealing between 600 and 800 °C undergoes an irreversible cubic-to-tetragonal phase transformation through oxidation–reduction reaction Cu¹⁺ + Mn⁴⁺  Cu²⁺ + Mn³⁺, and only tetrahedral Cu¹⁺ species in the cubic spinel shows this anomalous chemical shift. The negative shift of the core levels was correlated to an equal shift of the Cu 3d valence band levels. XPS valence bands from the samples annealed at different temperatures were compared to DOS calculations. The DOS computations were performed with FEFF-8.1 code using experimental crystal parameters established by the EXAFS analysis. It was found that the tetrahedral Cu¹⁺ in the 600 °C annealed sample exhibits localization of the 3d orbitals showing behavior characteristic to zinc. The completely filled and isolated 3d electron shell appears as a false valence band edge in the XPS spectrum. The position of the Cu 3d, and other core levels, is established by oxygen pinning the Cu valence band levels and by the fixed value of the p–d gap characteristic to the tetrahedral copper environment in this spinel.     

Superconducting oxide formation in the Yb---Ba---Cu---O system

Conditions for forming YbBa₂Cu₄O₈, Yb₂Ba₂Cu₃O_7−δ and YbBa₂Cu₃O_7−δ were determined in oxygen at 1.0 atm pressure by experiments with oxidized Yb---Ba---Cu---Ag alloys. YbBa₂Cu₃O_7−δ formed in less than 10 s when oxidized alloy ribbons were baked in the 805°C–890°C range. Large amounts of Ba₂Cu₃O₅ formed below 870°C. Yb₂Ba₄Cu₇O_15−δ and YbBa₂Cu₄O ₈ then formed in the 10²s–10³s range at temperatures in the 840°C–870°C and <840°C ranges, respectively. Ba₂Cu₃O₅ decomposition supplied Cu²⁺ and O²⁻ for the rapid transformation of YbBa₂Cu₃O_7−δ grains into Yb₂Ba₄Cu₇O_15−δ grains by intercalation. Intercalation was much slower in the absence of Ba₂Cu₃O₅. All of these transformation products underwent coarsening with increasing bake time. Rapid YbBa₂Cu₄O₈ and Yb₂Ba₄Cu₇O_15−δ formation, compared to the slow formation of these phase types when Yb was substituted by Y, Is due to the differing effects of Y and Yb on formation kinetics. Superconducting oxide-silver composite ribbons containing mainly YbBa₂Cu₃O_7−δ, Yb₂Ba₄Cu₇O_15−δ or YbBa₂Cu₄O₈ can be prepared from Yb---Ba ---Ba---Cu---Ag alloys.     

Designing a P2-type cathode material with Li in both Na and transition metal layers for Na-ion batteries

P2-type layered oxides have been considered as promising cathode materials for Na-ion batteries, but the capacity decay resulting from the Na⁺/vacancy ordering and phase transformation limits their future large-scale applications. Herein, the impact of Li-doping in different layers on the structure and electrochemical performance of P2-type Na_0.7Ni_0.35Mn_0.65O₂ is investigated. It can be found that Li ions successfully enter both the Na and transition metal layers. The strategy of Li-doping can improve the cycling stability and rate capability of P2-type layered oxides, which promotes the development of high-performance Na-ion batteries.     

A-site ordered perovskite CaCu_3Cu_2Ir_2O_(12-δ) with square-planar and octahedral coordinated Cu ions

A novel CaCu_3Cu_2Ir_2O_(12-δ) polycrystalline sample was synthesized at 8 GPa and 1373 K.Rietveld structural analysis shows that this compound crystallizes in an AA'_3B_4O_(12)-type A-site ordered perovskite structure with space group Im-3.Xray absorption spectra reveal a +2-charge state for both the square-planar and octahedral coordinated Cu ions,and the valence state of Ir is found to be about +5.Although the A-site Ca and the A'-site Cu~(2+) are 1:3 ordered at fixed atomic positions,the distribution of B-site Cu~(2+) and Ir~(5+) is disorderly.As a result,no long-range magnetic ordering is observed at temperatures down to 2 K.Electrical transport and heat capacity measurements demonstrate itinerant electronic behavior.The crystal structure is stable with pressure up to 35.7 GPa at room temperature.     

Oxygen permeability of La2Cu(Co)O4+δ solid solutions

Formation of the La₂Cu_1−xCo_xO_4+δ solid solutions with orthorhombic K₂NiF₄-type structure was found to be in the range of 0≤x≤0.30 at temperatures above 1270 K. Incorporating cobalt into the copper sublattice of lanthanum cuprate leads to increasing oxygen hyperstoichiometry and decreasing electrical conductivity. Thermal expansion coefficients of the La₂Cu_1−xCo_xO_4+δ (x=0.02–0.30) ceramics at 470–1100 K were calculated from the dilatometric data to vary in the range (12.2–13.2)×10⁻⁶ K⁻¹. Studying the dependence of oxygen permeation fluxes through La₂Cu(Co)O_4+δ on the membrane thickness demonstrated that the oxygen transport at the thickness values below 1 mm is limited by both surface exchange rate and bulk ionic conductivity. Oxygen permeability of the La₂Cu_1−xCo_xO_4+δ solid solutions was ascertained to increase with cobalt concentration at x=0.02–0.10 and to decrease with further dopant additions, indicating a participation of interstitial oxygen in the ionic transport.     

包钴铁氧体型γ-Fe2O3磁粉穆斯堡尔效应的研究

包钴铁氧体型,γ-Fe₂O₃磁粉(简记为CoFe-γ-Fe₂O₃)是针状γ-Fe₂O₃磁粉与Co⁺⁺和Fe⁺⁺溶液起反应,在每个针状颗粒上包覆了一层钴铁氧体固溶体。经此种方法处理后的γ-Fe₂O₃磁粉的矫顽力及其它磁特性有较大的提高。如矫顽力由原来415Oe增加到715Oe;剩磁和矫顽力随时间及温度变化小等。我们利用穆斯堡尔效应并配合其它研究手段进行了研究,认为:CoFe-γ-Fe₂O₃磁粉矫顽力的提高,主要是由于γ-Fe₂O₃磁粉表面包覆了一层钴铁氧体固溶体,γ-Fe₂O₃与钴铁氧体固溶体之间发生磁耦合作用之故。 关键词：     

Magnetic behavior of 3d dopants in superconducting REBa2Cu3−xFexO7+δ (RE=Dy, Er)

Mössbauer studies on ⁵⁷Fe-doped superconducting REBa₂Cu₃O_7+δ (RE=Er, Dy) were made as a function of temperature for x=0.15 and 0.30. The magnetic behavior of the 3d dopants, which mainly occupy Cu(1) sites, undergoes antiferromagnetic ordering which is coexistent with superconductivity at low temperature. The dimensionality of the magnetic interaction changes from 2D to 3D when the rare earth changes from Er to Dy. the line-widths of the Mössbauer subspectra are characteristic of magnetic fluctuation behavior in the vicinity of a phase transition. Combining these results with those of Fe-doped Y-123 (pseudo 1D) and Gd (3D), the magnitude of the rare earth moments appears to be strongly correlated with the dimensionality of the magnetic interaction of Fe dopants in these compounds. However, the Mössbauer spectrum for ¹⁵⁵Gd in GdBa₂Cu_2.85Fe_0.15O_7+δ (T_{N(Fe) 14 K}) shows no magnetic order at 4.9 K.     

First-principles study of electronic structure and magnetic properties of Sr3Fe2O5 oxide

We investigate the electronic structure and magnetic properties of layered compound Sr₃Fe₂O₅ based on first-principles calculations in the framework of density functional theory with GGA+U method. Under high pressure, the ladder-type layered structure of Sr₃Fe₂O₅ is transformed into the infinite layered structure accompanied by a transition from G-type anti-ferromagnetic (AFM) insulator to ferromagnetic (FM) metal and a spin transition from S=2 to S=1. We reproduce these transformations in our calculations and give a clear physical interpretation.     

Ni2O3掺杂对新固相源顶部籽晶熔渗生长法制备单畴GdBCO超导块材超导性能的影响

本文通过在新固相源中添加Ni₂O₃的方法, 采用顶部籽晶熔渗生长工艺(TSIG)制备出组分为(1-x) (Gd₂O₃+1.2BaCuO₂)+x Ni₂O₃、直径为20 mm的单畴GdBCO 超导块材(其中x = 0, 0.02, 0.06, 0.10, 0.14, 0.18, 0.30, 0.50 wt%), 并研究了Ni₂O₃的掺杂量x对样品的表面生长形貌、微观结构、临界温度T_c、磁悬浮力以及俘获磁通密度的影响. 研究结果表明, 当Ni₂O₃的掺杂量x在0–0.50 wt%的范围内时, 均可制备出单畴性良好的样品, 且Ni₂O₃的掺杂对样品中Gd211粒子的分布和粒径没有明显的影响. 在Ni₂O₃的掺杂量x从0增加到0.50 wt%的过程中, 样品的临界温度T_c呈现下降的趋势, 从x=0时的92.5 K下降到x=0.50 wt%时的86.5 K, 这是由于Ni^{3 +}替代GdBCO晶体中Cu^{2 +}所致; 样品磁悬浮力和俘获磁通密度均呈现先增大后减小的变化规律, x=0.14 wt%时, 磁悬浮力达到最大值34.2 N, x=0.10 wt%时, 俘获磁通密度达到最大值0.354 T. 样品磁悬浮力和俘获磁通密度的变化规律与Ni₂O₃的掺杂量x有密切关系, 只有当掺杂量x合适时, Ni³⁺对Cu^{2 +}的替代既不会造成T_c的明显下降, 但又能产生适量的Ni^{3 +}/Cu²⁺ 晶格畸变, 从而达到提高样品磁通钉扎能力和超导性能的效果.     

钙钛矿锰氧化物(La_(1-x)Eu_x)_(4/3)Sr_(5/3)Mn_2O_7(x=0,0.15)的磁性和电性研究

通过传统固相反应法制备了钙钛矿锰氧化物(La1-xEux)4/3Sr5/3Mn2O7(x=0,0.15)多晶样品,并且对其磁性和电性进行了研究.磁性测量表明:随着温度的降低,样品经历了一个复杂的转变过程,在温度为T*时经历二维短程铁磁有序转变,在温度为TC时进入三维长程铁磁态.随着Eu的掺杂,T*和TC减小,并且样品(La0.85Eu0.15)4/3Sr5/3Mn2O7在低温区表现出自旋玻璃行为.电性质测量表明:在母体La4/3Sr5/3Mn2O7中La位掺杂Eu后电阻率明显变大,金属绝缘转变温度TMI降低,磁电阻峰值增大.这些影响归因于较小的Eu3+离子替代La3+离子导致平均离子半径减小,晶格发生畸变.此外,较小的Eu3+离子优先占据层间岩盐层的R-site,使La3+,Sr3+,Eu3+离子在(La0.85Eu0.15)4/3Sr5/3Mn2O7中的分布更加有序,所以x=0.15的样品的ρ-T曲线只有一个峰.     

CuCl2/γ-Al2O3催化剂的EPR研究

通过测定Cu含量不同的新鲜CuCl₂/γ-Al₂O₃催化剂的EPR谱,以及对EPR谱的线型及强度的计算机处理和理论拟合等,研究了催化剂中CuCl₂在载体表面的分散方式,和Cu含量对Cu²⁺配位形式的影响.EPR结果表明,催化剂表面的Cu²⁺至少有两种不同配位状态.新鲜催化剂中所存在的两种不同谱线的比例决定了EPR谱的线型和强度,而两种谱线的比例又取决于催化剂中的Cu含量.在低Cu催化剂中Cu²⁺相互离散,倾向于形成富氧配位,具有较高的EPR强度,只有在Cu含量较高时,Cu²⁺才能形成富氯配位.鉴于低Cu催化剂不能与乙烯反应,而高Cu催化剂则可以使乙烯转化为二氯乙烷的事实,认为富氧配位的Cu²⁺可能具有与乙烯反应的活性.     

An electron spin resonance study of Eu doping effect in La_(4/3)Sr_(5/3)Mn_2O_7 single crystal

The effect of Eu3+ion doping in the La sites of single-crystal La4/3Sr5/3Mn2O7was investigated. Electron spin resonance(ESR) was applied to La4/3Sr5/3Mn2O7and(La0.8Eu0.2)4/3Sr5/3Mn2O7single crystals. A phase separation and phase transitions were observed from the ESR spectra data. Between 350 K and 300 K, both paramagnetic resonance(PMR)and anisotropic ferromagnetic resonance(FMR) lines were observed in the ab plane and the c axis direction, suggesting a coexistence of the paramagnetic(PM) phase and the ferromagnetic(FM) phase. The magnetization measurement reveals a spin-glass-like behavior in single-crystal(La0.8Eu0.2)4/3Sr5/3Mn2O7below the temperature of spin freezing Tf(～ 29.5 K).     

纳米微粒BaFe12O19掺杂对单畴超导块材GdBa2Cu3O7-δ性能的影响

磁通钉扎性能对GdBa₂Cu₃O_7-δ超导块材的实际应用具有重要的影响, 而引入合适的第二相粒子可以改善GdBa₂Cu₃O_7-δ 超导块材的磁通钉扎性能.本文采用顶部籽晶熔融织构法成功地制备出纳米微粒BaFe₁₂O₁₉(<100 nm)掺杂的超导块材, 样品的最终组分为Gd123+ 0.4 Gd211+ x BaFe₁₂O₁₉ (x=0, 0.2 mol%, 0.4 mol%, 0.8 mol%)+ 10 wt%Ag₂O+ 0.5 wt%Pt. 通过研究不同掺杂量的BaFe₁₂O₁₉微粒对GdBa₂Cu₃O_7-δ 超导块材微观结构和超导性能的影响, 结果表明当掺杂量为0.2 mol%时, 样品的临界电流密度几乎在整个外加磁场下都有明显的提高.在零场下, 临界电流密度达到5.5× 10⁴ A/cm². 纳米微粒BaFe₁₂O₁₉不仅可以保持掺杂前的化学组成, 作为有效的钉扎中心存在于超导块材中, 并且能够改善Gd₂BaCuO₅粒子的分布和细化Gd₂BaCuO₅粒子, 使Gd₂BaCuO₅粒子的平均粒径由未掺杂时的1.4 μ m减小到掺杂后的0.79 μ m, 进而提高了超导块材的临界电流密度和俘获磁场, 明显提高了GdBa₂Cu₃O_7-δ 超导块材的超导性能.临界温度T_C也有所提升, 并能够维持在92.5 K左右. 该结果为进一步研究纳米磁通钉扎中心的引入并改善GdBa₂Cu₃O_7-δ 超导块材的性能有着重要的意义.     

Electron concentration in YBa2Cu3O6.9 single crystals determined from field electron emission spectroscopic measurements

Results of field electron emission spectroscopic investigations of YBa₂Cu₃O_6.9 single crystal specimens oriented perpendicular to the c-axis are presented. It is shown that the shift of the total energy distribution of field-emitted electrons from YBa₂Cu₃O_6.9 along the energy scale with increasing electric-field strength at the surface of the specimen is due to the penetration of the electric field into the subsurface region of the YBa₂Cu₃O_6.9 specimen. The electron concentration in YBa₂Cu₃O_6.9 found from spectroscopic measurements is n=(2−4) × 10²¹ cm⁻³. Field electron emission spectroscopy and microscopy of YBa₂Cu₃O_6.9 allows one to draw the conclusion that the electron concentration in the bulk of the material does not change with cooling of specimens from 300 K to 115 K.     

Synthesis and properties of a new copper(II)-hafnium phosphate Cu0.5Hf2(PO4)3

Phosphates of general formula M_0.5Hf₂(PO₄)₃ with M=Cd²⁺, Ca²⁺, Sr²⁺ and Cu²⁺ were prepared by coprecipitation and characterized by several physical techniques. The compounds containing Cd²⁺, Ca²⁺, Sr²⁺ belong to the Nasicon-type structure, whereas Cu_0.5Hf₂(PO₄)₃ exhibited substantially different DRX patterns. Combined temperature programmed reduction (TPR) and temperature-programmed oxidation (TPO) showed that the copper in Cu_0.5Hf₂(PO₄)₃ was distributed between two energetically different sites in proportions respectively equal to 40 and 60%. Electron Paramagnetic Resonance (EPR) investigations confirmed the TPR/TPO results and revealed that the two sites hosting the Cu²⁺ ions are of orthorhombic symmetry. Moreover, the Cu²⁺ ions might be reduced by hydrogen to Cu⁺. These results were also supported by the UV–visible studies that showed the disappearance, under reducing conditions, of the band corresponding to crystal field transitions of Cu²⁺ ions and the emergence of a new peak attributed to the transitions between (3d)¹⁰ and (3d)⁹(4s)¹ Cu⁺ levels. At the same time, IR spectroscopy confirmed that protons entered the open lattice framework of the material and gave rise to a new protonated phase containing monovalent copper Cu_0.5^IH_0.5Hf₂(PO₄)₃. This redox process was proven to be reversible without any subsequent change in the network of the phosphate.     

Phase equilibria at low oxygen partial pressure in the Y---Ba---Cu---O system

The phase equilibria around YBa₂Cu₃O_7−x (123) and YBa₂Cu₄O₈ (124) phases at low oxygen partial pressure (1 atm) were investigated by X-ray diffraction and thermal analysis. The coexistence of 123 and 124 phase was confirmed under 1 atm oxygen pressure. By using the high temperature X-ray diffraction method, the univariant reaction YBa₂Cu₃O_7−x+Cu₂OY₂BaCu₂O₂+O₂ was identified. The oxygen partial pressure dependence of several univariant reactions has been investigated and the existence of two invariant reactions of L+O₂YBa₂Cu₃O_7−x+ BaCuO₂+CuO+Cu₂O and L+Y₂BaCuO₅+O₂YBa₂Cu₃O_7−x+CuO+Cu₂O was deduced to occur at 1103 K under 0.0032 atm O₂ and at 1143 K under 0.0085 atm O₂, respectively.     

钙钛矿锰氧化物(La1-xGdx)4/3Sr5/3Mn2O7 (x=0, 0.025) 磁性和输运性质研究

采用传统的高温固相烧结法制备了双层钙钛矿锰氧化物(La_1-xGd_x)_4/3Sr_5/3Mn₂ O₇ (x=0, 0.025)多晶样品. 通过X射线衍射仪研究发现样品为Sr₃Ti₂O₇型四方结构, 空间群为I4/mmm; 磁性测量表明, Gd³⁺掺杂后的样品(La_0.975Gd_0.025)_4/3Sr_5/3Mn₂O₇的三维磁有序转变温度(T_C1^3D)、磁化强度(M)均降低, 这是由于Gd³⁺的掺杂引起晶格的畸变, 从而使得晶格常数发生改变, 减弱了铁磁耦合而导致的; 通过电子自旋共振谱测量发现, 在T_C^3D<T<300 K温度范围内, 两样品在顺磁的基体上均有短程的铁磁团簇存在, 出现了相分离现象. 电性测量表明: 两样品分别在T_C1^3D (La_4/3Sr_5/3Mn₂O₇ 样品的三维磁有序转变温度, T_C0^3D)<T<300 K温度范围内均以三维变程跳跃的方式导电, 分析得出Gd³⁺的掺杂使得载流子局域长度的减小. 这表明载流子需要吸收更多的能量才能克服晶格的束缚进行跳跃, 因此(La_0.975Gd_0.025)_4/3Sr_5/3Mn₂ O₇ 样品的电阻较高.