Structural investigation of high-valent manganese-salen complexes by UV/Vis,Raman, XANES,and EXAFS spectroscopy

XANES and EXAFS spectroscopic studies at the Mn-K- and Br-K-edge of reaction products of (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) chloride ([(salen)Mn(III)Cl], 1) and (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) bromide ([(salen)Mn(III)Br], 2) with 4-phenylpyridine N-oxide (4-PPNO) and 3-chloroperoxybenzoic acid (MCPBA) are reported. The reaction of the Mn(III) complexes with two equivalents of 4-PPNO leads to a hexacoordinated compound, in which the manganese atom is octahedrally coordinated by four oxygen/nitrogen atoms of the salen ligand at an average distance of approximately 1.90 A and two additional, axially bonded oxygen atoms of the 4-PPNO at 2.25 A. The oxidation state of this complex was determined as approximately +IV by a comparative study of Mn(III) and Mn(V) reference compounds. The green intermediate obtained in reactions of MCPBA and solutions of 1 or 2 in acetonitrile was investigated with XANES, EXAFS, UV/Vis, and Raman spectroscopy, and an increase of the coordination number of the manganese atoms from 4 to 5 and the complete abstraction of the halide was observed. A formal oxidation state of IV was deduced from the relative position of the pre-edge 1s-->3d feature of the X-ray absorption spectrum of the complex. The broad UV/Vis band of this complex in acetonitrile with lambda(max)=648 nm was consistent with a radical cation structure, in which a MCPBA molecule was bound to the Mn(IV) central atom. An oxomanganese(V) or a dimeric manganese(IV) species was not detected.     

Novel Gel—like Process for Synthesizing Submicron LiaNi0.8Co0.2O2 Powders Used in Lithium Ion Batteries

A novel gel-like process has been developed for synthesizing LiaNi0.8Co0.2O2 powders,using citric acid as a chelating agent. This process improves the homogeneity of constituent cation and enhances their reactivity in the obtained precursor. The results of electrochemical test demonstrated that these materials exhibited excellent electrochemical properties. Its initial capacity reached 181.6 mAh/g and reversible efficiency at the first cycle is about 88.6%.     

用于空间BIB探测器的0.3 W@4.2 K大冷量轻量化低温系统

大阵列BIB探测器由于其高量子效率和低暗电流而成为广泛的研究对象,特别是在空间应用方向。如2021年发射的詹姆斯韦伯太空望远镜,它已经进行了许多重要的天文观测。一个稳定、高效、轻量化的液氦温区低温系统对BIB探测器的运行至关重要。氦节流制冷机可取代传统的大容积液氦杜瓦,能满足空间液氦温区的制冷要求。为了同时提高4.2 K的制冷量并减轻重量,提出了一种0.3 W@4.2 K的大冷量轻量化的4.2 K低温制冷系统。并且在现有0.1 W@4.1 K制冷量的低温系统上进行实验,验证了该系统的设计方法。在不同的冷却温度区采用不同的冷却方法,以实现冷却的高效性和轻便性。开发了一个新的集成斯特林制冷机,在80 K时提供高效的一级预冷,制冷量为15 W,重量仅为4.5 kg;二级预冷采用主动活塞调相的15 K脉管制冷机,制冷量为0.9 W。此多级低温制冷系统通过耦合氦气JT循环,可以在4.2 K时提供0.3 W的制冷量,输入功低于1.8 kW。此系统将为正在快速发展的红外天文观测所需的空间BIB探测器提供保障。     

Unlocking the Capacity of Vanadium Oxide by Atomically Thin Graphene-Analogous V2O5·nH2O in Aqueous Zinc-Ion Batteries

Aqueous Zn-ion batteries (AZIBs) are promising due to their high theoretical energy density and intrinsic safety, and the natural abundance of Zn. Since low voltage is an intrinsic shortage of AZIBs, achieving super-high capacity of cathode materials is a vital way to realize high practical energy density, which however remains a huge challenge. Herein, the capacity increase of classical vanadium oxide cathode is predicted via designing atomic thickness of 2D structure to introduce abundant Zn²⁺ storage sites based on density functional theory (DFT) calculation; then graphene-analogous V₂O₅·nH₂O (GAVOH) with only few atomic layers is fabricated, realizing a record capacity of 714 mAh g⁻¹. Pseudocapacitive effect is unveiled to mainly contribute to the super-high capacity due to the highly exposed GAVOH external surface. In situ Raman and synchrotron X-ray techniques unambiguously uncover the Zn²⁺ storage mechanism. Carbon nanotubes (CNTs) are further introduced to design GAVOH-CNTs gel ink for large-scale cathode fabrication. The hybrid cathode demonstrates ultra-stable cycling and excellent rate capability and delivers a high energy density of 476 Wh kg⁻¹ at 76 W kg⁻¹; 228 Wh kg⁻¹ is still retained at high mass loading of 10.2 mg cm⁻². This work provides inspiration for breaking the capacity limit of cathode in AZIBs.     

Hydrofluoric Acid-Removable Additive Optimizing Electrode Electrolyte Interphases with Li+ Conductive Moieties for 4.5 V Lithium Metal Batteries

High-voltage lithium metal batteries (LMBs) are capable to achieve the increasing energy density. However, their cycling life is seriously affected by unstable electrolyte/electrode interfaces and capacity instability at high voltage. Herein, a hydrofluoric acid (HF)-removable additive is proposed to optimize electrode electrolyte interphases for addressing the above issues. N, N-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) aniline (DMPATMB) is used as the electrolyte additive to induce PF₆⁻ decomposition to form a dense and robust LiF-rich solid electrolyte interphase (SEI) for suppressing Li dendrite growth. Moreover, DMPATMB can help to form highly Li⁺ conductive Li₃N and LiBO₂, which can boost the Li⁺ transport across SEI and cathode electrolyte interphase (CEI). In addition, DMPATMB can scavenge traced HF in the electrolyte to protect both SEI and CEI from the corrosion. As expected, 4.5 V Li|| LiNi_0.6Co_0.2Mn_0.2O₂ batteries with such electrolyte deliver 145 mAh g⁻¹ after 140 cycles at 200 mA g⁻¹. This work provides a novel insight into high-voltage electrolyte additives for LMBs.     

Inorganic Filler Enhanced Formation of Stable Inorganic-Rich Solid Electrolyte Interphase for High Performance Lithium Metal Batteries

Lithium metal (LM) is a promising anode material for next generation lithium ion based electrochemical energy storage devices. Critical issues of unstable solid electrolyte interphases (SEIs) and dendrite growth however still impede its practical applications. Herein, a composite gel polymer electrolyte (GPE), formed through in situ polymerization of pentaerythritol tetraacrylate with fumed silica fillers, is developed to achieve high performance lithium metal batteries (LMBs). As evidenced theoretically and experimentally, the presence of SiO₂ not only accelerates Li⁺ transport but also regulates Li⁺ solvation sheath structures, thus facilitating fast kinetics and formation of stable LiF-rich interphase and achieving uniform Li depositions to suppress Li dendrite growth. The composite GPE-based Li||Cu half-cells and Li||Li symmetrical cells display high Coulombic efficiency (CE) of 90.3% after 450 cycles and maintain stability over 960 h at 3 mA cm⁻² and 3 mAh cm⁻², respectively. In addition, Li||LiFePO₄ full-cells with a LM anode of limited Li supply of 4 mAh cm⁻² achieve capacity retention of 68.5% after 700 cycles at 0.5 C (1 C = 170 mA g⁻¹). Especially, when further applied in anode-free LMBs, the carbon cloth||LiFePO₄ full-cell exhibits excellent cycling stability with an average CE of 99.94% and capacity retention of 90.3% at the 160th cycle at 0.5 C.     

Catalytically Induced Robust Inorganic-Rich Cathode Electrolyte Interphase for 4.5 V Li||NCM622 Batteries

Tailoring inorganic components of cathode electrolyte interphase (CEI) and solid electrolyte interphase (SEI) is critical to improving the cycling performance of lithium metal batteries. However, it is challenging due to complicated electrolyte reactions on cathode/anode surfaces. Herein, the species and inorganic component content of the CEI/SEI is enriched with an objectively gradient distribution through employing pentafluorophenyl 4-nitrobenzenesulfonate (PFBNBS) as electrolyte additive guided by engineering bond order with functional groups. In addition, a catalytic effect of LiNi_0.6Mn_0.2Co_0.2O₂ (NCM622) cathode is proposed on the decomposition of PFBNBS. PFBNBS with lower highest occupied molecular orbital can be preferentially oxidized on the NCM622 surface with the help of the catalytic effect to induce an inorganic-rich CEI for superior electrochemical performance at high voltage. Moreover, PFBNBS can be reduced on the Li surface due to its lower lowest unoccupied molecular orbital , increasing inorganic moieties in SEI for inhibiting Li dendrite generation. Thus, 4.5 V Li||NCM622 batteries with such electrolyte can retain 70.4% of initial capacity after 500 cycles at 0.2 C, which is attributed to the protective effect of the excellent CEI on NCM622 and the inhibitory effect of its derived CEI/SEI on continuous electrolyte decomposition.     

A Materials Perspective on Direct Recycling of Lithium-Ion Batteries: Principles,Challenges and Opportunities

As the dominant means of energy storage technology today, the widespread deployment of lithium-ion batteries (LIBs) would inevitably generate countless spent batteries at their end of life. From the perspectives of environmental protection and resource sustainability, recycling is a necessary strategy to manage end-of-life LIBs. Compared with traditional hydrometallurgical and pyrometallurgical recycling methods, the emerging direct recycling technology, rejuvenating spent electrode materials via a non-destructive way, has attracted rising attention due to its energy efficient processes along with increased economic return and reduced CO₂ footprint. This review investigates the state-of-the-art direct recycling technologies based on effective relithiation through solid-state, aqueous, eutectic solution and ionic liquid mediums and thoroughly discusses the underlying regeneration mechanism of each method regarding different battery chemistries. It is concluded that direct regeneration can be a more energy-efficient, cost-effective, and sustainable way to recycle spent LIBs compared with traditional approaches. Additionally, it is also identified that the direct recycling technology is still in its infancy with several fundamental and technological hurdles such as efficient separation, binder removal and electrolyte recovery. In addressing these remaining challenges, this review proposes an outlook on potential technical avenues to accelerate the development of direct recycling toward industrial applications.     

Tetrabutylammonium Bromide Functionalized Ti3C2Tx MXene as Versatile Cathode Buffer Layer for Efficient and Stable Inverted Perovskite Solar Cells

2D Ti₃C₂T_x MXene, possessing facile preparation, high electrical conductivity, flexibility, and solution processability, shows good application potential for enhancing device performance of perovskite solar cells (PVSCs). In this study, tetrabutylammonium bromide functionalized Ti₃C₂T_x (TBAB-Ti₃C₂T_x) is developed as cathode buffer layer (CBL) to regulate the PCBM/Ag cathode interfacial property for the first time. By virtue of the charge transfer from TBAB to Ti₃C₂T_x demonstrated by electron paramagnetic resonance and density functional theory, the TBAB-Ti₃C₂T_x CBL with high electrical conductivity exhibits significantly reduced work function of 3.9 eV, which enables optimization of energy level alignment and enhancement of charge extraction. Moreover, the TBAB-Ti₃C₂T_x CBL can effectively inhibit the migration of iodine ions from perovskite layer to Ag cathode, which synergistically suppresses defect states and reduce charge recombination. Consequently, utilizing MAPbI₃ perovskite without post-treatment, the TBAB-Ti₃C₂T_x based device exhibits a dramatically improved power conversion efficiency of 21.65% with significantly improved operational stability, which is one of the best efficiencies reported for the devices based on MAPbI₃/PCBM with different CBLs. These results indicate that TBAB-Ti₃C₂T_x shall be a promising CBL for high-performance inverted PVSCs and inspire the further applications of quaternary ammonium functionalized MXenes in PVSCs.     

基于高密度子网格光线追迹的三维发射层析重建算法

三维(three- dimensional,3D) 发射层析技术(emission computerized tomography,ECT) 是一种简单、高效且准确的燃 烧场3D成像与检测技术,其中权重矩阵的计算 精度决定了层析重建的精度和质量。本文研究了一种基于高密度子网格光线追迹的权重矩阵 计算方法, 将被测区域划分为密度更高的子网格,并根据相机成像模型实现光线追迹,以确定离散网格 对投影像素 的权重因子。数值模拟和燃烧火焰重建实验表明该算法具有较高的精度和计算效率。该研究 对于3D发射层析技术的实用化具有重要的理论意义。