Mg-doped layered oxide cathode for Na-ion batteries

Na-ion batteries (NIBs) are regarding as the optimum complement for Li-ion batteries along with the rapid development of stationary energy storage systems. In order to meet the commercial demands of cathodes for NIBs, O3-type Cu containing layered oxide Na_0.90Cu_0.22Fe_0.30Mn_0.48O₂ with good comprehensive performance and low-cost element components is very promising for the practical use. However, only part of the Cu³⁺/Cu²⁺ redox couple participated in the redox reaction, thus impairing the specific capacity of the cathode materials. Herein, Mg²⁺-doped O3-Na_0.90Mg_0.08Cu_0.22Fe_0.30Mn_0.40O₂ layered oxide without Mn³⁺ was synthesized successfully, which exhibited improved reversible specific capacity of 118 mAh/g in the voltage range of 2.4-4.0 V at 0.2 C, corresponding to the intercalation/deintercalation of 0.47 Na⁺ (0.1 more than that of Na_0.90Cu_0.22Fe_0.30Mn_0.48O₂). This work demonstrates an important strategy to obtain advanced layered oxide cathodes for NIBs.     

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.     

A strategy to improve the electrochemical performance of Ni-rich positive electrodes: Na/F-co-doped LiNi_(0.6)Mn_(0.2)Co_(0.2)O_2

Ni-rich layered lithium transition metal oxides LiNi_xMn_yCo_zO_2(1-y-z ≥ 0.6) are promising candidates for cathode materials, but their practical applications are hindered by high-voltage instability and fast capacity fading. Using density functional theory calculations, we demonstrate that Na-, F-doping, and Na/F-co-doping can stabilize the structure and result into a higher open circuit voltage than pristine LiNi_(0.6)Mn_(0.2)Co_(0.2)O_2(NMC622) during the charging process, which may attain greater discharge capacity. F doping may inhibit the diffusion of Li ions at the beginning and end of charging; Na doping may improve Li ion diffusion due to the increase in Li layer spacing, consistent with prior experiments. Na/F-codoping into NMC622 promotes rate performance and reduces irreversible phase transitions for two reasons:(i) a synergistic effect between Na and F can effectively restrain the Ni/Li mixing and then enhances the mobility of Li ions and(ii) Ni/Li mixing hinders the Ni ions to migrate into Li layers and thus, stabilizes the structure. This study proposes that a layer cathode material with high electrochemical performance can be achieved via rational dopant modification, which is a promising strategy for designing efficient Li ion batteries.     

First-principles study on β-GeS monolayer as high performance electrode material for alkali metal ion batteries

Based on the density functional theory calculations, we have investigated the feasibility of two-dimensional β-GeS monolayer as high-performance anodes for alkali metal ion batteries. The results show that the electrical conductivity of β-GeS monolayer can be enhanced after adsorbing the alkali metal atoms owing to the semiconductor-to-metal transition. The low diffusion barriers of alkali metal atoms on the β-GeS surface indicate a rapid charge/discharge rate without metal clustering. Moreover, the low average open-circuit voltage (0.211 V) and a high theoretical capacity (1024 mAh·g^-1) for Na suggest that the β-GeS monolayer is a promising anode material for Na-ion batteries with high performance.     

Electrochromic & magnetic properties of electrode materials for lithium ion batteries

Progress in electrochromic lithium ion batteries(LIBs) is reviewed, highlighting advances and possible research directions. Methods for using the LIB electrode materials' magnetic properties are also described, using several examples.Li_4Ti_5O_(12)(LTO) film is discussed as an electrochromic material and insertion compound. The opto-electrical properties of the LTO film have been characterized by electrical measurements and UV–Vis spectra. A prototype bi-functional electrochromic LIB, incorporating LTO as both electrochromic layer and anode, has also been characterized by charge–discharge measurements and UV–Vis transmittance. The results show that the bi-functional electrochromic LIB prototype works well. Magnetic measurement has proven to be a powerful tool to evaluate the quality of electrode materials. We introduce briefly the magnetism of solids in general, and then discuss the magnetic characteristics of layered oxides, spinel oxides, olivine phosphate Li Fe PO_4, and Nasicon-type Li_3Fe_2(PO_4)_3. We also discuss what kind of impurities can be detected, which will guide us to fabricate high quality films and high performance devices.     

New layered metal oxides as positive electrode materials for room-temperature sodium-ion batteries

In order to achieve better Na storage performance, most layered oxide positive electrode materials contain toxic and expensive transition metals Ni and/or Co, which are also widely used for lithium-ion batteries. Here we report a new quaternary layered oxide consisting of Cu, Fe, Mn, and Ti transition metals with O3-type oxygen stacking as a positive electrode for room-temperature sodium-ion batteries. The material can be simply prepared by a high-temperature solidstate reaction route and delivers a reversible capacity of 94 m Ah/g with an average storage voltage of 3.2 V. This paves the way for cheaper and non-toxic batteries with high Na storage performance.     

La1.3Sr1.7Mn2O7/SrTiO3-Nb异质结的整流和光伏特性

采用脉冲激光沉积法在SrTiO₃:0.7%Nb(100)单晶衬底上生长了La_1.3Sr_1.7Mn₂O₇(LSMO)薄膜, 并 研究了LSMO/SrTiO₃-Nb异质结的输运性质和光伏效应. 研究发现, 异质结具有良好的整流特征和明显的光生伏特效应. 在532 nm激光辐照下, 光生电压随温度升高先增大后减小, 并且在150 K达到最大值400 mV, 此温度点与LSMO薄膜发生金属-绝缘体转变的温度一致, 这表明异质结的光生伏特效应受LSMO薄膜内部的输运特征调控. 进一步, 从光生电压随时间的变化曲线中分析发现, 上升沿符合一阶指数函数, 这与载流子的迁移过程相关; 而下降沿符合二阶指数函数, 这与结两侧载流子的外部回路中和以及材料内部的电子-空穴湮灭有关. 值得注意的是, 上升沿和下降沿的时间常数均随着温度先增大后减小, 且最大值均出现在LSMO薄膜的金属-绝缘转变温度.     

Removal of rhodamine B from aqueous solutions using vanadium pentoxide/titanium butyl oxide hybrid xerogels

A stable and insoluble V_2O_5·n H_2O/tetra-n-butyl titanate(TBO) hybrid xerogel was synthesized by the sol–gel method. This novel material proved to be an efficient absorbent with an absorption capacity of 179 mg·g~(-1)for Rhodamine B(Rh B) in water due to its unique layered structure, which can effectively accommodate Rh B molecules between its layers as demonstrated by XRD and FTIR spectroscopic analyses.     

Nanoscale surface modification of Li-rich layered oxides for high-capacity cathodes in Li-ion batteries

Li-rich layered oxides (LLOs) have been developed as a high-capacity cathode material for Li-ion batteries, but the structural complexity and unique initial charging behavior lead to several problems including large initial capacity loss, capacity and voltage fading, poor cyclability, and inferior rate capability. Since the surface conditions are critical to electrochemical performance and the drawbacks, nanoscale surface modification for improving LLO’s properties is a general strategy. This review mainly summarizes the surface modification of LLOs and classifies them into three types of surface pre-treatment, surface gradient doping, and surface coating. Surface pre-treatment usually introduces removal of Li₂O for lower irreversible capacity while surface doping is aimed to stabilize the structure during electrochemical cycling. Surface coating layers with different properties, protective layers to suppress the interface side reaction, coating layers related to structural transformation, and electronic/ionic conductive layers for better rate capability, can avoid the shortcomings of LLOs. In addition to surface modification for performance enhancement, other strategies can also be investigated to achieve high-performance LLO-based cathode materials.     

新型交生结构自掺杂铁基超导体

铁基高温超导体的基本结构单元是反萤石型Fe₂X₂层（X为磷族或硫族元素）,因此,设计具有Fe₂X₂层的新化合物成为探索铁基超导材料的有效途径.本文在回顾铁基超导体结构特征和基本结构类型的基础上,归纳总结了铁基超导体块层结构设计的基本原则;着重介绍迄今发现的几类具有层状交生（intergrowth）结构的新型自掺杂铁基超导材料.     

TiS2-graphene heterostructures enabling polysulfide anchoring and fast electrocatalyst for lithium-sulfur batteries: A first-principles calculation

Lithium-sulfur batteries have attracted attention because of their high energy density. However, the "shuttle effect" caused by the dissolving of polysulfide in the electrolyte has greatly hindered the widespread commercial use of lithium-sulfur batteries. In this paper, a novel two-dimensional TiS₂/graphene heterostructure is theoretically designed as the anchoring material for lithium-sulfur batteries to suppress the shuttle effect. This heterostructure formed by the stacking of graphene and TiS₂ monolayer is the van der Waals type, which retains the intrinsic metallic electronic structure of graphene and TiS₂ monolayer. Graphene improves the electronic conductivity of the sulfur cathode, and the transferred electrons from graphene enhance the polarity of the TiS₂ monolayer. Simulations of the polysulfide adsorption show that the TiS₂/graphene heterostructure can maintain good metallic properties and the appropriate adsorption energies of 0.98-3.72 eV, which can effectively anchor polysulfides. Charge transfer analysis suggests that further enhancement of polarity is beneficial to reduce the high proportion of van der Waals (vdW) force in the adsorption energy, thereby further enhancing the anchoring ability. Low Li₂S decomposition barrier and Li-ion migration barrier imply that the heterostructure has the ability to catalyze fast electrochemical kinetic processes. Therefore, TiS₂/graphene heterostructure could be an important candidate for ideal anchoring materials of lithium-sulfur batteries.     

The effect of S-functionalized and vacancies on V2C MXenes as anode materials for Na-ion and Li-ion batteries

The electrochemical properties of V₂C and V₂CT₂ (T = O, S) MXenes with and without vacancy as anode materials for Na-ion and Li-ion batteries, have been studied using first-principles calculation. The present results indicate that the adsorption strength of Li-ion and Na-ion on V₂CS₂ are less than that of O-functionalized, together with a lower diffusion barrier. Simultaneously, V₂CS₂ monolayer exhibits lower open-circuit voltage (OCV) values of 0.72 and 0.49 V for Li- and Na-ion, respectively. Interestingly, the presence of atomic vanadium vacancy on V₂CS₂ monolayer exerts more prominent effects on enhancing adsorption strength than that of carbon vacancy for Li-ion and Na-ion, but with an exception for the diffusion of Li-ion and Na-ion on V₂CS₂ monolayer. The finding suggests that the V₂CS₂ monolayer is expected to be a potential candidate as anode material for Li-ion and Na-ion battery due to its lower open-circuit voltages and diffusion barriers.     

Li掺杂少层MoS2的电荷分布及与石墨和氮化硼片的比较

基于第一性原理计算, 研究了Li掺杂的少层(1-3层) MoS₂的电荷分布, 并与石墨片和BN片的电荷分布特征进行了比较. 与石墨片和BN片相同的是: 电荷转移的大部分只发生在Li与最靠近Li的第一层MoS₂之间. 然而, 第二层和第三层MoS₂也能获得10%的转移电荷, 而石墨片和BN片的第二层和第三层得不到2%的电荷. 结合静电能和功函数的分析可知, MoS₂、石墨片和BN片的电荷分布主要由层间的静电相互作用和功函数来决定. 这些研究结果对于揭示具有多层结构的电荷分布特征及其电子器件的设计提供了理论支持.     

Composition dependence of oxide anion conduction in the BIMEVOX family

Partial substitution for vanadium in Bi₄V₂O₁₁ can lead to the stabilization at room temperature of one of the three polymorphs , β, γ exhibited by the mother compound. A tentative classification of the BIMEVOX phases based on these structural polytypes is carried out, and a review of the different identified ways to stabilize the γ-type phases, the most performant ones in term of oxide anion conduction, is proposed. The experimental results clearly indicate that the predominant parameter is not the size or the valence state of the dopant, but rather the structural parameter correlated with the ability for the dopant to regularize the diffusion slab between the Bi₂O₂ sheets in these layered materials.     

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.     

Pressure dependence of the thermal stability in LiMn2O4

Structural stability in terms of the decomposition temperature in LiMn₂O₄ was systematically investigated by a series of high-temperature and high-pressure experiments.LiMn₂O₄ was found to have structural stability up to 5 GPa at room temperature.Under ambient pressure,the compound decomposed at 1300℃.The decomposition temperature decreased with increasing pressure,yielding more complex decomposed products.Below the decomposition temperature,the crystal structure of LiMn₂O₄ varied with pressure.The presented results in this study offer new insights into the thermal and pressure stability of LiMn₂O₄ materials as a cathode for lithium-ion batteries that can operate under extreme conditions.Therefore,these findings may serve as a useful guide for future work for improving lithium-ion batteries.     

Observation of pseudogap in SnSe2 atomic layers grown on graphite

Superconducting metal dichalcogenides (MDCs) present several similarities to the other layered superconductors like cuprates. The superconductivity in atomically thin MDCs has been demonstrated by recent experiments, however, the investigation of the superconductivity intertwined with other orders are scarce. Investigating the pseudogap in atomic layers of MDCs may help to understand the superconducting mechanism for these true two-dimensional (2D) superconducting systems. Herein we report a pseudogap opening in the tunneling spectra of thin layers of SnSe₂ epitaxially grown on highly oriented pyrolytic graphite (HOPG) with scanning tunneling microscopy/spectroscopy (STM/STS). A significant V-shaped pseudogap was observed to open near the Fermi level (E_F) in the STS. And at elevated temperatures, the gap gradually evolves to a shallow dip. Our experimental observations provide direct evidence of a pseudogap state in the electron-doped SnSe₂ atomic layers on the HOPG surface, which may stimulate further exploration of the mechanism of superconductivity at 2D limit in MDCs.     

A 62 K superconductor with an original structure: Sr4−xBaxTlCu2CO3O7

A new superconductor with an original structure, Sr_4−xBa_xTlCu₂CO₃O₇ has been isolated for 1≤x≤2. It crystallizes in a A-type space group with a=3.84 Å≈a_p, b≈8 × a_p, c≈17.0 Å. The HREM study of this new curprate shows that it derives from the Tl_0.5Pb_0.5Sr₄Cu₂CO₃O₇ structure by a shearing mechanism. Indeed, it can be described as ribbons of the latter structure, four octahedra thick, shifted c/2 with respect to each other. It results in infinite single perovskite layers waving along the (001) plane and connected through flat mixed layers [(TIO)₄(CO)₄]∞. This oxycarbonate can also be described as a 1201-type structure in which the [TIO]∞ layers are replaced by mixed [(TIO)₄(CO)₄]∞ layers. The susceptibility measurements show that this cuprate exhibits a significantly higher critical temperature than the 1201-cuprates. The T_{c onset} of the synthesized phase is 56 K and it can be increased up to 62 K by hydrogen annealing; in the same way, one observes a large Meissner volume fraction of 35% at 4.2 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.     

112型铁基化合物EuFeAs2的单晶生长与表征

铁基超导体中含有一类特殊的112型结构化合物,其层状结构中含有一层锯齿形的As链构型.本文报道了用CsCl助熔剂法生长新型铁基112型EuFeAs₂母体单晶的具体方法,以及对该单晶的结构和物性的详细表征.通过能量色散X射线能谱扫描对单晶样品进行的化学成分分析,以及单晶X射线衍射的结构解析,确定该单晶样品属于EuFeAs₂相,结构精修得到EuFeAs₂具有空间群为Imm2（No.44）的正交晶体结构,晶格常数分别是a=21.285（9）Å,b=3.9082（10）Å,c=3.9752（9）Å.通过低温电阻测量,发现在110 K附近和46 K附近存在两个异常电阻跳变.进一步分析表明,110 K附近存在两个邻近的相变,这两个相变与铁基母体材料中常见的结构相变和Fe²⁺的反铁磁相变相符合.结合磁化率测量分析,可知46 K附近的相变属于Eu²⁺的反铁磁相变.