Lithiation MXene Derivative Skeletons for Wide-Temperature Lithium Metal Anodes

Lithium (Li) metal, as an appealing candidate for the next-generation of high-energy-density batteries, is plagued by its safety issue mainly caused by uncontrolled dendrite growth and infinite volume expansion. Developing new materials that can improve the performance of Li-metal anode is one of the urgent tasks. Herein, a new MXene derivative containing pure rutile TiO₂ and N-doped carbon prepared by heat-treating MXene under a mixing gas, exhibiting high chemical activity in molten Li, is reported. The lithiation MXene derivative with a hybrid of LiTiO₂-Li₃N-C and Li offers outstanding electrochemical properties. The symmetrical cell assembling lithiation MXene derivative hybrid anode exhibits an ultra-long cycle lifespan of 2000 h with an overpotential of ≈30 mV at 1 mA cm⁻², which overwhelms Li-based anodes reported so far. Additionally, long-term operations of 34, 350, and 500 h at 10 mA cm⁻² can be achieved in symmetrical cells at temperatures of −10, 25, and 50 °C, respectively. Both experimental tests and density functional theory calculations confirm that the LiTiO₂-Li₃N-C skeleton serves as a promising host for Li infusion by alleviating volume variation. Simultaneously, the superlithiophilic interphase of Li₃N guides Li deposition along the LiTiO₂-Li₃N-C skeleton to avoid dendrite growth.     

退火温度对新型锆合金薄板带材析出相和织构的影响

采用扫描电镜和超高分辨透射电镜,对具有良好冲制性能的新型锆合金薄板成品带材进行含晶粒、第二相粒子等在内的显微组织研究,并探索真空退火处理条件下温度对带材显微组织的影响。结果显示:新型锆合金薄板成品带材晶粒平均尺寸2.17 μm,存在{0001}<1010>和{0001}<1120>两种织构,大部分晶粒<1120>平行带材RD方向,较少晶粒<1010>平行带材RD方向;第二相粒子分布在晶粒内部及晶界,平均尺寸114 nm,尺寸较大的为不规则椭圆形的Zr-Nb-Fe相,尺寸较小的为圆形的β-Nb相;热处理退火温度降低,带材晶粒尺寸减小,第二相粒子细小弥散分布;新型锆合金薄板成品带材良好冲制性能主要源于轧制积累应变诱发再结晶过程进行充分,导致晶粒细小及孪晶发生破碎;相对轧制变形,退火对带材冲制性能影响不显著。     

Unsteady free convection of second‐grade nanofluid with a new time‐space fractional heat conduction

The Caputo and Caputo–Fabrizio derivative are applied to study a second‐grade nanofluid over a vertical plate. A comparative analysis is presented to study the unsteady free convection of a second‐grade nanofluid with a new time–space fractional heat conduction. The governing equations with mixed time–space fractional derivatives are non‐dimensionalized and solved numerically, and a comparison between the Caputo and the Caputo–Fabrizio models is made. It is found that the temperature is higher for the Caputo–Fabrizio fractional model than the Caputo model, but the higher velocity only exists near the vertical plate for the Caputo–Fabrizio model than the Caputo model. Moreover, the velocity for the Caputo model will exceed the Caputo–Fabrizio model as y evolves.     

基于向下延拓Milne法的重力归一化总梯度法

重力归一化总梯度法需进行向下延拓和垂向导数的计算，这两个过程都会放大高波数成分，影响计算结果的稳定性。为此，将向下延拓Milne法及积分垂向二阶导数法引入重力归一化总梯度的计算。将该方法应用于估算无限长水平圆柱体模型的中心位置，计算结果准确。然后针对实测重力数据，利用本方法得到的矿洞中心埋深较基于泰勒级数展开的重力归一化总梯度法更准确，因此本文方法具有一定的实用性。     

Noncentrosymmetric Tetrel Pnictides RuSi4P4 and IrSi3P3: Nonlinear Optical Materials with Outstanding Laser Damage Threshold

Noncentrosymmetric (NCS) tetrel pnictides have recently generated interest as nonlinear optical (NLO) materials due to their second harmonic generation (SHG) activity and large laser damage threshold (LDT). Herein nonmetal-rich silicon phosphides RuSi₄P₄ and IrSi₃P₃ are synthesized and characterized. Their crystal structures are reinvestigated using single crystal X-ray diffraction and ²⁹Si and ³¹P magic angle spinning NMR. In agreement with previous report RuSi₄P₄ crystallizes in NCS space group P1, while IrSi₃P₃ is found to crystallize in NCS space group Cm, in contrast with the previously reported space group C2. A combination of DFT calculations and diffuse reflectance measurements reveals RuSi₄P₄ and IrSi₃P₃ to be wide bandgap (E_g) semiconductors, E_g = 1.9 and 1.8 eV, respectively. RuSi₄P₄ and IrSi₃P₃ outperform the current state-of-the-art infrared SHG material, AgGaS₂, both in SHG activity and laser inducer damage threshold. Due to the combination of high thermal stabilities (up to 1373 K), wide bandgaps (≈2 eV), NCS crystal structures, strong SHG responses, and large LDT values, RuSi₄P₄ and IrSi₃P₃ are promising candidates for longer wavelength NLO materials.     

Charge Transportation and Chirality in Liquid Crystalline Helical Network Phases of Achiral BTBT-Derived Polycatenar Molecules

First examples of multichain (polycatenar) compounds, based on the π-conjugated [1]benzothieno[3,2-b]benzothiophene unit are designed, synthesized, and their soft self-assembly and charge carrier mobility are investigated. These compounds, terminated by the new fan-shaped 2-brominated 3,4,5-trialkoxybenzoate moiety, form bicontinuous cubic liquid crystalline (LC) phases with helical network structure over extremely wide temperature ranges (>200 K), including ambient temperature. Compounds with short chains show an achiral cubic phase with the double network, which upon increasing the chain length, is at first replaced by a tetragonal 3D phase and then by a mirror symmetry is broken triple network cubic phase. In the networks, the capability of bypassing defects provides enhanced charge carrier mobility compared to imperfectly aligned columnar phases, and the charge transportation is non-dispersive, as only rarely observed for LC materials. At the transition to a semicrystalline helical network phase, the conductivity is further enhanced by almost one order of magnitude. In addition, a mirror symmetry broken isotropic liquid phase is formed beside the 3D phases, which upon chain elongation is removed and replaced by a hexagonal columnar LC phase.     

High-entropy oxide phases with magnetoplumbite structure

Sintering of oxides and carbonates at 1400 °C gives crystalline high-entropy single phase products with a BaFe₁₂O₁₉ (magnetoplumbite) structure containing 5 doping elements at high concentration level: Ba(Fe₆Ti_1·2Co_1·2In_1.2Ga_1.2Cr_1.2)O₁₉. The complete list of explored substitutions includes K, Ca, Sr, Pb, La, Bi, Al, Ga, In, Ti, V, Cr, Mn, Co, and Ni. Loading to the batch more than 5 dopants or introduction of NiO, or V₂O₅ initiates formation of second phases like spinels or vanadates. Bi₂O₃ and K₂O are too volatile at sintering temperature and were evaporated from the samples.Due to large ionic radius, the In³⁺ cation is likely to be incorporated not only on Fe³⁺ sites, but also on Ba²⁺ sites, that follow from resulting crystal composition. The smallest di-valent and tri-valent cations, Sr²⁺ and Al³⁺, are found to preferably concentrate together in the same magnetoplumbite phase crystals within one sample.According to elemental analysis of selected hexagonal crystals in the investigated 8 doped samples the most prospective compositions for obtaining high-entropy single phase with magnetoplumbite structure can be formulated as (Ca,Sr,Ba,Pb,La)Fe_x(Al,Ga,In,Ti,Cr,Mn,Co)_12-xO₁₉ where x = 1.5–6.     

Generalised multivariable supertwisting algorithm

The purpose of this paper is to present an extension of the generalised supertwisting algorithm (STA) to the multivariable framework. We begin by introducing an algorithm that may be deemed as a linear, quasicontinuous, or discontinuous multivariable system, depending on the functions that define them. For the class represented by such an algorithm we prove the robust, Lyapunov stability of the origin and characterise the perturbations that preserve its stability. In particular, when its vector field is discontinuous or quasicontinuous our algorithm is endowed with finite‐time stability. Due to its resemblance to the scalar case, we denote such finite‐time stable systems as generalised multivariable STA. Furthermore, the class of finite‐time stable systems comprise the currently available versions of STAs. To finalise, by means of simulation examples, we show that our proposed finite‐time stable algorithms are well suited for signals online differentiation and highlight their dynamical traits.