Local Electronic Structure Modulation Enables Fast-Charging Capability for Li-Rich Mn-Based Oxides Cathodes With Reversible Anionic Redox Activity

Anionic and cationic redox chemistries boost ultrahigh specific capacities of Li-rich Mn-based oxides cathodes (LRMO). However, irreversible oxygen evolution and sluggish kinetics result in continuous capacity decay and poor rate performance, restricting the commercial fast-charging cathodes application for lithium ion batteries. Herein, the local electronic structure of LRMO is appropriately modulated to alleviate oxygen release, enhance anionic redox reversibility, and facilitate Li⁺ diffusion via facile surface defect engineering. Concretely, oxygen vacancies integrated on the surface of LRMO reduce the density of states of O 2p band and trigger much delocalized electrons to distribute around the transition metal, resulting in less oxygen release, enhancing reversible anionic redox and the MnO₆ octahedral distortion. Besides, partially reduced Mn and lattice vacancies synchronously stimulate the electrochemical activity and boost the electronic conductivity, Li⁺ diffusion rate, and fast charge transfer. Therefore, the modified LRMO exhibits enhanced cyclic stability and fast-charging capability: a high discharging capacity of 212.6 mAh·g⁻¹ with 86.98% capacity retention after 100 cycles at 1 C is obtained and to charge to its 80%, SOC is shortened to 9.4 min at 5 C charging rate. This work will draw attention to boosting the fast-charging capability of LRMO via the local electronic structure modulation.     

In Situ Deformation Topology of COFs with Shortened Channels and High Redox Properties for Li–S Batteries

Covalent organic frameworks (COFs) with various topologies are typically synthesized by selecting and designing connecting units with rich shapes. However, this process is time-consuming and labour-intensive. Besides, the tight stacking of COFs layers greatly restrict their structural advantages. It is crucial to effectively exploit the high porosity and active sites of COFs by topological design. Herein, for the first time, inducing in situ topological changes in sub-chemometric COFs by adding graphene oxide (GO) without replacing the monomer, is proposed. Surprisingly, GO can slow down the intermolecular stacking and induce rearrangement of COFs nanosheets. The channels of D- [4+3] COFs are significantly altered while the stacking of periodically expanded framework is weakened. This not only maximizes the exposure of pore area and polar groups, but also shortens the channels and increases the redox activity, which enables high loading while enhancing host-guest interactions. This topological transformation to exhibit the structural features of COFs for efficient application is an innovative molecular design strategy.     

High-rate Decoupled Water Electrolysis System Integrated with α-MoO3 as a Redox Mediator with Fast Anhydrous Proton Kinetics

Hydrogen is a promising alternative to fossil fuels that can reduce greenhouse gas emissions. Decoupled water electrolysis system using a reversible proton storage redox mediator, where the oxygen evolution reaction and hydrogen evolution reaction are separated in time and space, is an effective approach to producing hydrogen gas with high purity, high flexibility, and low cost. To realize fast hydrogen production in such a system, a redox mediator capable of releasing protons rapidly is required. Herein, α-MoO₃, with an ultrafast proton transfer property that can be explained by a dense hydrogen bond network in the lattice oxygen arrays of HxMoO₃, is examined as a high-rate redox mediator for fast hydrogen production in acidic electrolytes. The α-MoO₃ redox mediator shows both a large capacity of 204 mAh g⁻¹ and fast hydrogen production at a current rate of 10 A cm⁻²(≈153 A g⁻¹), outperforming most of the previously reported solid-state redox mediators.     

Voltage Decay of Li-Rich Layered Oxides: Mechanism,Modification Strategies,and Perspectives

Li-rich layered oxides (LLOs) have been considered as the most promising cathode materials for achieving high energy density Li-ion batteries. However, they suffer from continuous voltage decay during cycling, which seriously shortens the lifespan of the battery in practical applications. This review comprehensively elaborates and summarizes the state-of-the-art of the research in this field. It is started from the proposed mechanism of voltage decay that refers to the phase transition, microscopic defects, and oxygen redox or release. Furthermore, several strategies to mitigate the voltage decay of LLOs from different scales, such as surface modification, elemental doping, regulation of components, control of defect, and morphology design are summarized. Finally, a systematic outlook on the real root of voltage decay is provided, and more importantly, a potential solution to voltage recovery from electrochemistry. Based on this progress, some effective strategies with multiple scales will be feasible to create the conditions for their commercialization in the future.     

Comprehensively Strengthened Metal-Oxygen Bonds for Reversible Anionic Redox Reaction

Introducing anionic redox in layered oxides is an effective approach to breaking the capacity limit of conventional cationic redox. However, the anionic redox reaction generally suffers from excessive oxidation of lattice oxygen to O₂ and O₂ release, resulting in local structural deterioration and rapid capacity/voltage decay. Here, a Na_0.71Li_0.22Al_0.05Mn_0.73O₂ (NLAM) cathode material is developed by introducing Al³⁺ into the transition metal (TM) sites. Thanks to the strong Al–O bonding strength and small Al³⁺ radius, the TMO₂ skeleton and the holistic TM–O bonds in NLAM are comprehensively strengthened, which inhibits the excessive lattice oxygen oxidation. The obtained NLAM exhibits a high reversible capacity of 194.4 mAh g^-1 at 20 mA g^-1 and decent cyclability with 98.6% capacity retention over 200 cycles at 200 mA g⁻¹. In situ characterizations reveal that the NLAM experiences phase transitions with an intermediate OP4 phase during the charge–discharge. Theoretical calculations further confirm that the Al substitution strategy is beneficial for improving the overlap between Mn 3d and O 2p orbitals. This finding sheds light on the design of layered oxide cathodes with highly reversible anionic redox for sodium storage.     

Differential Electrochemical Conductance Imaging at the Nanoscale

Electron transfer in proteins is essential in crucial biological processes. Although the fundamental aspects of biological electron transfer are well characterized, currently there are no experimental tools to determine the atomic‐scale electronic pathways in redox proteins, and thus to fully understand their outstanding efficiency and environmental adaptability. This knowledge is also required to design and optimize biomolecular electronic devices. In order to measure the local conductance of an electrode surface immersed in an electrolyte, this study builds upon the current–potential spectroscopic capacity of electrochemical scanning tunneling microscopy, by adding an alternating current modulation technique. With this setup, spatially resolved, differential electrochemical conductance images under bipotentiostatic control are recorded. Differential electrochemical conductance imaging allows visualizing the reversible oxidation of an iron electrode in borate buffer and individual azurin proteins immobilized on atomically flat gold surfaces. In particular, this method reveals submolecular regions with high conductance within the protein. The direct observation of nanoscale conduction pathways in redox proteins and complexes enables important advances in biochemistry and bionanotechnology.     

钒流电池用磺化聚芴醚酮-聚苯胺原位表面复合质子交换膜的制备

质子交换膜是液流电池的核心部件之一。文中以磺化聚芴醚酮(SPFEK)膜为基膜,采用稀溶液化学氧化聚合法在SPFEK膜表面原位复合一层聚苯胺,通过调整苯胺(An)单体的浓度,制得SPFEK/PANI复合膜。采用扫描电镜与红外光谱表征了复合膜的结构,表明聚苯胺已经成功地在SPFEK膜表面复合。通过钒流单电池的性能测试,结果表明,当苯胺单体的浓度为0.05 mol/L时,所制备的复合质子交换膜具有最高的H+传导选择性,所组装的钒流电池具有最好的自放电性能,在充放电流为50 m A/cm~2时,电池的库仑效率、电压效率、能量效率分别达到95%,83%,75%。     

化学因子分析法测定液体推进剂A

基于测定推进剂Ａ现有分析方法准确度低,神经网络法对仪器要求高等不足,提出了的一种新的分析方法。该方法利用已知酸的电位滴定数据建立多元线性回归数学模型,利用化学因子分解该模型,对未知样进行浓度测定。实际测定结果表明本方法的最大分析误差不超过０．１７％,标准偏差不超过１．９％,满足样品分析要求。     

多元分析法在沉淀滴定中的应用

将多元分析法应用于沉淀滴定之中 ,提出固定电位的方法 ,建立了沉淀滴定中各组分浓度与体积之间关系的数学模型 ,对卤素和硫氰酸盐混合体系进行了测定。