锰离子氧化沉淀法实现锂离子电池LiNi0.8Co0.05Mn0.15O2材料的回收和利用

以浓盐酸为浸出剂,以NaOH和NH₄HCO₃为沉淀剂,利用Mn²⁺在碱性条件下的氧化反应改变离子的沉淀次序进而分步回收的方案,探究了浓盐酸酸浸处理三元正极材料LiNi_0.8Co_0.05Mn_0.15O₂的最佳条件。在分步沉淀过程中,Mn²⁺被氧化为不溶于非还原性酸的MnO （OH）₂,并在酸性条件下回收。Ni、Co则在碱性条件下利用NaOH回收,而Li则利用NH₄HCO₃回收。该方法中Mn的回收率达到85.1%,产品纯度达到98.6%; Li的回收率达到95.0%,产品纯度达到99.3%。由回收材料重新合成的三元正极组装的软包电池的首圈放电比容量达到了175 mAh·g^-1,可以以超过99.5%的库仑效率稳定循环50圈。     

锂电池中的“锂键”效应

由于广泛存在,氢键在化学领域备受重视。“锂键”具有类似于氢键的一些性质,但锂的金属性和相对较大的原子半径,又使得“锂键”具有自己独特的一些特征。在氢键的基础上,介绍了“锂键”的概念、结构特点及其在锂电池中的应用,有助于人们深刻理解和应用“锂键”。考虑到“锂键”的新概念目前在化学教学中还较少涉及,期望今后可以适当增加“锂键”化学的相关知识,紧跟科技发展的潮流,进一步培养学生的科研创新意识。     

Highly Selective Transmembrane Transport of Exogenous Lithium Ions through Rationally Designed Supramolecular Channels

Lithium ions have been applied in the clinic in the treatment of psychiatric disorders. In this work, we report artificial supramolecular lithium channels composed of pore-containing small aromatic molecules. By adjusting the lumen size and coordination numbers, we found that one of the supramolecular channels developed shows unprecedented transmembrane transport of exogenous lithium ions with a Li⁺/Na⁺ selectivity ratio of 23.0, which is in the same level of that of natural Na⁺ channels. Furthermore, four coordination sites inside channels are found to be the basic requirement for ion transport function. Importantly, this artificial lithium channel displays very low transport of physiological Na⁺, K⁺, Mg²⁺, and Ca²⁺ ions. This highly selective Li⁺ channel may become an important tool for studying the physiological role of intracellular lithium ions, especially in the treatment of psychiatric disorders.     

Radiation-sensitive nanogel-incorporated Fricke hydrogel dosimeters with reduced diffusion rates

Fricke gel dosimeters have great potential for three-dimensional (3D) dose verification in radiation therapy; however, they suffer from time-dependent ion diffusion after irradiation, severely affecting their stability and reliability. In this work, a pullulan-based amphiphilic molecule was synthesized, characterized, and self-assembled into nanogels. Nanogel structures were embedded into gel dosimeters to reduce the diffusion rates, and radiation-sensitive nanogel-incorporated Fricke hydrogel nanocomposites were prepared successfully. The results demonstrated that the diffusion coefficient of improved dosimeters was reduced to 0.125 ± 0.001 mm² h⁻¹, while maintaining the high optical dose sensitivity (0.0410 ± 0.0004 Gy⁻¹ cm⁻¹). It provides a powerful tool toward the practical application of 3D dosimeters.     

A Gel Polymer Electrolyte with 2D Filler-reinforced for Dendrite Suppression Li-Ion Batteries

Gel polymer electrolytes (GPEs) incorporate both the high ionic conductivity of organic liquid electrolyte and the high safety performance of all-solid-state electrolytes (ASSEs), greatly improving the electrochemical performance of solid polymer electrolytes (SPEs). However, the practical application of GPEs is still limited by inferior interface compatibility, lithium dendrites, etc. Herein, we prepared GPEs based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) further co-blended the two-dimensional sheet inorganic filler hectorite and poly(methyl methacrylate) (PMMA) to improve the mechanical and electrochemical properties of the GPEs. When the content of PMMA and hectorite is optimal, this GPEs have an ionic conductivity of 1.06×10⁻³ S cm⁻¹ and outstanding lithium symmetric cells cycle time of more than 3000 h, indicating that the introduction of filler effectively inhibits the growth of lithium dendrites at room temperature. Moreover, the GPEs adopt a relatively simple solution casting method to provide a fresh idea for the synthesis of high-performance GPEs.     

Ion transmission in an electrospray ionization-mass spectrometry interface using an S-lens

We present the design and performance of an in-house built electrospray ionization-mass spectrometry (ESI-MS) interface equipped with an S-lens ion guide. The ion source was designed specifically for our ion beam experiments to investigate the chemical reactivity and deposition of the clusters and nanoparticles. It includes standard ESI-MS interface components, such as nanoelectrospray, ion transfer capillary, and the S-lens. A custom design enables systematic optimization of all relevant factors influencing ion formation and transfer through the interface. By varying the ESI voltage and flow rate, we determined the optimal operating conditions for selected silica emitters. A comparison of the pulled silica emitters with different tip inner diameters reveals that the total ion current is highest for the largest tip, whereas a tip with the smallest diameter exhibited the highest transmission efficiency through the ESI-MS interface. Ion transmission through the transfer capillary is strongly limited by its length, but the loss of ions can be reduced by increasing the capillary voltage and temperature. The S-lens was characterized over a wide range of RF frequencies and amplitudes. Maximum ion current was detected at RF amplitudes greater than 50 V peak-to-peak (p/p) and frequencies above 750 kHz, with a stable ion transmission region of about 20%. A factor of 2.6 increase in total ion current is observed for 650 kHz as RF amplitudes reach 400 V p/p. Higher RF amplitudes also focus the ions into a narrow beam, which mitigates their losses when passing through the ion guide.     

Prussian Blue Modified Amperometric Hg2+ Ion Biosensor Based on Glucose Oxidase Inhibition

In this research a Hg²⁺ ion biosensor was developed by combining Prussian blue (PB) with glucose oxidase (GOx) – an enzyme that can be inhibited by Hg²⁺ ions. An application of PB in the design of Hg²⁺ ion biosensor enabled detecting changes in hydrogen peroxide reduction current at low operational potential of 0.2 vs Ag|AgCl,KCl_sat. The described Hg²⁺ ion biosensor exhibited wide linear range from 27 μM to 247 μM of Hg²⁺ and higher maximal detectable concentration of Hg²⁺ than other GOx inhibition-based biosensors, making it convenient for the analysis of samples with high concentration of Hg²⁺ ions.     

In Situ Polymerized 1,3-Dioxolane Electrolyte for Integrated Solid-State Lithium Batteries

Solid-state lithium batteries are promising and safe energy storage devices for mobile electronics and electric vehicles. In this work, we report a facile in situ polymerization of 1,3-dioxolane electrolytes to fabricate integrated solid-state lithium batteries. The in situ polymerization and formation of solid-state dioxolane electrolytes on interconnected carbon nanotubes (CNTs) and active materials is the key to realizing a high-performance battery with excellent interfacial contact among CNTs, active materials and electrolytes. Therefore, the electrodes could be tightly integrated into batteries through the CNTs and electrolyte. Electrons/ions enable full access to active materials in the whole electrode. Electrodes with a low resistance of 4.5 Ω □⁻¹ and high lithium-ion diffusion efficiency of 2.5×10⁻¹¹ cm² s⁻¹ can significantly improve the electrochemical kinetics. Subsequently, the batteries demonstrated high energy density, amazing charge/discharge rate and long cycle life.     

Hydrogen Bond Networks Stabilized High-Capacity Organic Cathode for Lithium-Ion Batteries

High-capacity small organic materials are plagued by their high solubility. Here we proposed constructing hydrogen bond networks (HBN) via intermolecular hydrogen bonds to suppress the solubility of active material. The illustrated 2, 7- diamino-4, 5, 9, 10-tetraone (PTO-NH₂) molecule with intermolecular hydrogen (H) bond between O in −C=O and H in −NH₂, which make PTO-NH₂ presents transverse two-dimensional extension and longitudinal π–π stacking structure. In situ Fourier transform infrared spectroscopy (FTIR) has tracked the reversible evolution of H-bonds, further confirming the existence of HBN structure can stabilize the intermediate 2-electron reaction state. Therefore, PTO-NH₂ with HBN structure has higher active site utilization (95 %), better cycle stability and rate performance. This study uncovers the H-bond effect and evolution during the electrochemical process and provides a strategy for materials design.     

Grain Boundary Electronic Insulation for High-Performance All-Solid-State Lithium Batteries

Sulfide electrolytes with high ionic conductivities are one of the most highly sought for all-solid-state lithium batteries (ASSLBs). However, the non-negligible electronic conductivities of sulfide electrolytes (≈10⁻⁸ S cm⁻¹) lead to electron smooth transport through the sulfide electrolyte pellets, resulting in Li dendrite directly depositing at the grain boundaries (GBs) and serious self-discharge. Here, a grain-boundary electronic insulation (GBEI) strategy is proposed to block electron transport across the GBs, enabling Li−Li symmetric cells with 30 times longer cycling life and Li−LiCoO₂ full cells with three times lower self-discharging rate than pristine sulfide electrolytes. The Li−LiCoO₂ ASSLBs deliver high capacity retention of 80 % at 650 cycles and stable cycling performance for over 2600 cycles at 0.5 mA cm⁻². The innovation of the GBEI strategy provides a new direction to pursue high-performance ASSLBs via tailoring the electronic conductivity.