Eliminating Transition Metal Migration and Anionic Redox to Understand Voltage Hysteresis of Lithium‐Rich Layered Oxides

Lithium‐rich layered oxides are promising candidate cathode materials for the Li‐ion batteries with energy densities above 300 Wh kg^?1. However, issues such as the voltage hysteresis and decay hinder their commercial applications. Due to the entanglement of the transition metal (TM) migration and the anionic redox upon lithium extraction at high potentials, it is difficult to recognize the origin of these issues in conventional Li‐rich layered oxides. Herein, Li₂MoO₃ is chosen since prototype material to uncover the reason for the voltage hysteresis as the TM migration and anionic redox can be eliminated below 3.6 V versus Li⁺/Li in this material. On the basis of comprehensive investigations by neutron powder diffraction, scanning transmission electron microscopy, synchrotron X‐ray absorption spectroscopy, and density functional theory calculations, it is clarified that the ordering–disordering transformation of the Mo₃O₁₃ clusters induced by the intralayer Mo migration is responsible for the voltage hysteresis in the first cycle; the hysteresis can take place even without the anionic redox or the interlayer Mo migration. A similar suggestion is drawn for its iso‐structured Li₂RuO₃ (C2/c). These findings are useful for understanding of the voltage hysteresis in other complicated Li‐rich layered oxides.     

Enhanced Stability of Perovskite Solar Cells Incorporating Dopant‐Free Crystalline Spiro‐OMeTAD Layers by Vacuum Sublimation

The main handicap still hindering the eventual exploitation of organometal halide perovskite‐based solar cells is their poor stability under prolonged illumination, ambient conditions, and increased temperatures. This article shows for the first time the vacuum processing of the most widely used solid‐state hole conductor (SSHC), i.e., the Spiro‐OMeTAD [2,2′,7,7′‐tetrakis (N,N‐di‐p‐methoxyphenyl‐amine) 9,9′‐spirobifluorene], and how its dopant‐free crystalline formation unprecedently improves perovskite solar cell (PSC) stability under continuous illumination by about two orders of magnitude with respect to the solution‐processed reference and after annealing in air up to 200 °C. It is demonstrated that the control over the temperature of the samples during the vacuum deposition enhances the crystallinity of the SSHC, obtaining a preferential orientation along the π–π stacking direction. These results may represent a milestone toward the full vacuum processing of hybrid organic halide PSCs as well as light‐emitting diodes, with promising impacts on the development of durable devices. The microstructure, purity, and crystallinity of the vacuum sublimated Spiro‐OMeTAD layers are fully elucidated by applying an unparalleled set of complementary characterization techniques, including scanning electron microscopy, X‐ray diffraction, grazing‐incidence small‐angle X‐ray scattering and grazing‐incidence wide‐angle X‐ray scattering, X‐ray photoelectron spectroscopy, and Rutherford backscattering spectroscopy.     

Nonuniform Ionic and Electronic Transport of Ceramic and Polymer/Ceramic Hybrid Electrolyte by Nanometer‐Scale Operando Imaging for Solid‐State Battery

Replacing the liquid electrolyte in lithium batteries with solid‐state ion conductor is promising for next‐generation energy storage that is safe and has high energy density. Here, nanometer‐resolution ionic and electronic transport imaging of Li₃PS₄ (LPS), a solid‐state electrolyte (SSE), is reported. This nm resolution is achieved by using a logarithm‐scale current amplifier that enhances the current sensitivity to the fA range. Large fluctuations of ion current—one to two orders of magnitude on the LPS and on the LPS region of a polymer/LPS bulk hybrid SSE—that must be mitigated to eliminate Li dendrite formation and growth, are found. This ion current fluctuation is understood in terms of highly anisotropic transport kinetic barriers along the different crystalline axes due to different grain orientations in the polycrystalline and glass ceramic materials. The results on the bulk hybrid SSE show a sharp transition of ionic and electronic transport at the LPS/polymer boundary and decreases in average ionic current with decreasing polyimine particle size and with extensive cycling. The results elucidate the mechanism of polyimine extension into interparticles to prevent Li dendrite growth. This work opens up novel characterization of charge transport, which relates to Li plating and stripping for solid‐state‐batteries.     

Conductive Li3.08Cr0.02Si0.09V0.9O4 Anode Material: Novel “Zero‐Strain” Characteristic and Superior Electrochemical Li+ Storage

“Zero‐strain” compounds are ideal energy‐storage materials for long‐term cycling because they present negligible volume change and significantly reduce the mechanically induced deterioration during charging–discharging. However, the explored “zero‐strain” compounds are very limited, and their energy densities are low. Here, γ phase Li_3.08Cr_0.02Si_0.09V_0.9O₄ (γ‐LCSVO) is explored as an anode compound for lithium‐ion batteries, and surprisingly its “zero‐strain” Li⁺ storage during Li⁺ insertion–extraction is found through using various state‐of‐the‐art characterization techniques. Li⁺ sequentially inserts into the 4c(1) and 8d sites of γ‐LCSVO, but its maximum unit‐cell volume variation is only ≈0.18%, the smallest among the explored “zero‐strain” compounds. Its mean strain originating from Li⁺ insertion is only 0.07%. Consequently, both γ‐LCSVO nanowires (γ‐LCSVO‐NW) and micrometer‐sized particles (γ‐LCSVO‐MP) exhibit excellent cycling stability with 90.1% and 95.5% capacity retention after as long as 2000 cycles at 10C, respectively. Moreover, γ‐LCSVO‐NW and γ‐LCSVO‐MP respectively deliver large reversible capacities of 445.7 and 305.8 mAh g^?1 at 0.1C, and retain 251.2 and 78.4 mAh g^?1 at 10C. Additionally, γ‐LCSVO shows a suitably safe operating potential of ≈1.0 V, significantly lower than that of the famous “zero‐strain” Li₄Ti₅O₁₂ (≈1.6 V). These merits demonstrate that γ‐LCSVO can be a practical anode compound for stable, high‐energy, fast‐charging, and safe Li⁺ storage.     

A 3D Lithium/Carbon Fiber Anode with Sustained Electrolyte Contact for Solid‐State Batteries

To reconcile the energy storage ability and operational safety of lithium metal batteries (LMBs), a transformation from a liquid to a solid‐state system is required. However, Li volume variation, poor interfacial contact, and high operation temperatures hinder its practical applications. To address the above issues, here, an integral structure design for solid‐state LMBs is shown, in which a Li‐preinfused 3D carbon fiber (Li/CF) anode is ionically connected to a cathode via an autopolymerized gel electrolyte. The gel electrolyte helps to encapsulate the liquid electrolyte within the Li/CF anode and the cathode to improve the interfacial contact. The gel also serves as a reservoir that balances the liquid electrolyte supply during repeated Li stripping/plating process. As a result, the symmetrical cells and full cells with Li/CF electrodes exhibit improved cycling stability and effective suppression of dendrites at ambient temperature. This work facilitates the realization of solid‐state LMBs with high energy and high safety.     

The deposition of CENH3 in maize is stringently regulated

The centromere, as an essential element to mediate chromosome segregation, is epigenetically determined by CENH3‐containing nucleosomes as a functional marker; therefore the accurate deposition of CENH3 is crucial for chromosome transmission. We characterized the deposition of CENH3 in maize by over‐expression and mutational analysis. Our results revealed that over‐expressing CENH3 in callus is lethal while over‐expressing GFP‐CENH3 and CENH3‐YFP in callus and plants is not and can be partly deposited normally. Different mutations of GFP‐CENH3 demonstrated that CENH3‐Thr4 in the N‐terminus was needed for the deposition as a positive phosphorylation site and the last five amino acids in the C‐terminus are necessary for deposition. The C‐terminal tail of CENH3 is confirmed to be responsible for the interaction of CENH3 and histone H4, which indicates that CENH3 maintains deposition in centromeres via interacting with H4 to form stable nucleosomes. For GFP‐CENH3 and CENH3‐YFP, the fused tags at the termini probably affect the structure of CENH3 and reduce its interaction with other proteins, which in turn could decrease proper deposition. Taken together, multiple amino acids or motifs were shown to play essential roles in CENH3 deposition, which is suggested to be affected by numerous factors in maize.     

水氮添加对内蒙古温带典型草原植被氮含量季节和年际动态的影响

作为对全球变化响应最敏感的生态系统类型之一,草原生态系统植被氮含量的季节、年际变化及其对气候变化(氮沉降、降水格局改变)的响应研究相对匮乏。基于内蒙古温带典型草原5年的氮添加(10 g N m~(-2) a~(-1))和水添加(添加量80 mm,分2 mm×40次、5 mm×16次、10 mm×8次、20 mm×4次、40 mm×2次5种处理)控制试验分析了水氮添加后植被氮含量在生态系统和物种两个水平的季节和年际变化。结果表明,高强度水添加处理有降低(10 mm/次和40 mm/次)生态系统氮含量的趋势,但不显著,小强度水添加处理(2 mm/次、5 mm/次)在不同年份之间无一致的升高或降低趋势,但所有水添加处理有降低两种优势物种整个生长季氮含量的趋势。氮添加促进生态系统和两种优势物种整个生长季的氮含量,但该促进作用可被水添加抵消,且这种抵消作用随水氮添加年限的延长而加剧。水氮添加均增加了生态系统氮含量的年际变异,但对特定物种季节内变异的影响在湿润和干旱年份存在一定差异。本研究将为预测草原生态系统对未来氮沉降增加和降水格局改变的响应及模型改进提供科学依据。     

施氮对森林生态系统AM真菌群落组成及多样性的影响

丛枝菌根（AM）真菌能够和绝大多数陆生植物形成互惠共生体,具有重要的生态功能。在氮（N）沉降日益严重的背景下,越来越多的土壤生态学家开始关注N沉降对AM真菌群落的影响,然而已有研究大多数集中在草地生态系统,对森林生态系统的关注相对较少,而在森林生态系统开展的模拟研究又多采用林下施N的方式,忽略了冠层发生的一系列生态过程,可能无法准确反映真实情形。依托鸡公山野外控制试验平台,采用高通量测序技术就不同施N方式（林下vs林冠）及速率对AM真菌alpha多样性和群落组成的影响进行了连续4 a的监测。试验综合考虑植被、坡向和坡度等因素,采用完全随机区组设计,包括4个区组（重复）,每个区组随机设置5个样方,对应5个不同处理：对照（CK）、林冠施N 25 kg hm^-2 a^-1（CN25）和50 kg hm^-2 a^-1（CN50）、林下施N 25 kg hm^-2 a^-1（UN25）和50 kg hm^-2 a^-1（UN50）。结果发现,在目前的N素添加水平和时间尺度上,施N方式和施N速率对AM真菌的alpha多样性都没有显著影响,二者之间也无交互作用。然而,经过一年的试验处理,施N方式对AM真菌群落组成产生了轻微的影响,而施N速率有极显著的影响,且二者之间存在显著交互作用。当施N速率为25 kg hm^-2 a^-1时,林冠施N和对照相比差异不显著,而林下施N处理AM真菌群落组成与对照相比差异极显著,与林冠施N相比,差异也极显著;当施N速率为50 kg hm^-2 a^-1时,林冠施N与对照处理群落组成有略微差异（P=0.080）,林下施N与林冠施N及对照处理相比AM真菌群落组成均没有显著变化。在接下来的三年中,施N方式和施N速率对AM真菌的群落组成都没有显著影响,二者之间也无显著交互作用。这说明在特定的施N速率和处理时间下,林下施N可能会高估自然N沉降对AM真菌群落组成的影响。随着处理时间的延长,不同处理下AM真菌群落有趋同的趋势,可能是因为AM真菌群落对N沉降产生了适应性。本研究评估了施N方式对森林生态系统AM真菌群落组成与结构的影响,在未来的研究中需要设定更多的N素梯度和更长的时间跨度,才能够更全面的认识N沉降的生态效应。