无黏结剂HZSM-5沸石催化稀乙醇脱水制乙烯

分别以低硅有黏结剂HZSM-5沸石(硅铝比约30)与无黏结剂HZSM-5沸石为催化剂,考察了它们在稀乙醇脱水制乙烯(ETE)反应中的催化性能。实验结果表明,后者具有较高的活性,且在反应温度低于260℃时,乙烯选择性和收率较高。对比了3种不同骨架硅铝比的无黏结剂HZSM-5沸石催化剂(Z435,Z92,Z31,骨架硅铝比分别为435,92,31)在ETE反应中的催化性能,发现随骨架硅铝比的增加,催化剂的活性降低。分别以HCl溶液、水蒸气及水蒸气-HCl溶液相结合处理的方法对Z31催化剂进行改性,以调节其吸附性质及表面酸量,并对比了不同方法改性的Z31催化剂的活性,发现水蒸气-HCl溶液相结合处理的Z31催化剂的活性最高,在235℃时乙醇转化率达到99.0%,乙烯选择性及收率分别达到98.0%和97.0%。     

钠离子电池无粘结剂二氧化钛负极材料的合成

作为电池的重要组成部分,电极材料直接影响电池的能量密度。电极材料在制作过程中往往会添加粘结剂以稳定极片结构,但粘结剂的加入会降低电极材料的比容量,影响其离子迁移速率。通过在经水热反应刻蚀的钛箔/网上原位生长二氧化钛(TiO 2)得到无粘结剂TiO 2/Ti纳米线阵列电极,并系统地研究不同钛基底及水热反应温度对TiO 2/Ti纳米线阵列电极物理性能和电化学性能的影响。结果表明,不同钛基底及水热反应温度均对生长的TiO 2纳米线的形貌和电化学性能有重要影响。其中通过220℃水热反应生长在钛网(0.15 mm)上的TiO 2纳米线呈蛛网状,具有较大的比表面积,属于锐钛矿型TiO 2,储钠过程主要由赝电容效应控制,且具有优秀的电化学性能:首周放电比容量为986 mAh g^-1,库伦效率为21.7%;随后放电比容量逐渐稳定在240 mAh g^-1左右;循环200周后放电比容量仍能达到228 mAh g^-1,库伦效率稳定在99.3%左右;即使在3200 mA g^-1的超大电流密度下,放电比容量仍能达到152 mAh g^-1。无粘结剂电极材料极大可以有限地提升电极材料的比容量,对未来高能量密度电池体系的设计具有一定的理论意义和参考价值。     

Interconnected Metallic Membrane Enabled by MXene Inks Toward High-Rate Anode and High-Voltage Cathode for Li-Ion Batteries

The ever-increasing popularity of smart electronics demands advanced Li-ion batteries capable of charging faster and storing more energy, which in turn stimulates the innovation of electrode additives. Developing single-phase conductive networks featuring excellent mechanical strength/integrity coupled with efficient electron transport and durability at high-voltage operation should maximize the rate capability and energy density, however, this has proven to be quite challenging. Herein, it is shown that a 2D titanium carbide (known as MXene) metallic membrane can be used as single-phase interconnected conductive binder for commercial Li-ion battery anode (i.e., Li₄Ti₅O₁₂) and high-voltage cathodes (i.e., Ni_0.8Mn_0.1Co_0.1O₂). Electrodes are fabricated directly by slurry-casting of MXene aqueous inks composited with active materials without any other additives or solvents. The interconnected metallic MXene membrane ensures fast charge transport and provides good durability, demonstrating excellent rate performance in the Li//Li₄Ti₅O₁₂ cell (90 mAh g⁻¹ at 45 C) and high reversible capacity (154 mAh g⁻¹ at 0.2 C/0.5 C) in Li//Ni_0.8Mn_0.1Co_0.1O₂ cell coupled with high-voltage operation (4.3 V vs Li/Li⁺). The LTO//NMC full cell demonstrates promising cycling stability, maintaining capacity retention of 101.4% after 200 cycles at 4.25 V (vs Li/Li⁺) operation. This work provides insights into the rational design of binder-free electrodes toward acceptable cyclability and high-power density Li-ion batteries.     

木质纤维的冷冻活化及其制备无胶板材

利用氢氧化钠-聚乙二醇-尿素混合溶液对木质纤维进行冷冻活化处理,然后制备无胶纤维板,通过对比无胶胶合纤维板力学性能,确定木质纤维较佳冷冻活化工艺,并利用傅里叶变换红外光谱、X射线衍射分析、差式扫描量热分析、热重分析、X射线光电子能谱分析对木质纤维的冷冻活化效果进行表征。研究结果表明:木质纤维较佳冷冻活化工艺为氢氧化钠、聚乙二醇、尿素的质量比7∶4.2∶12,活化剂质量(以氢氧化钠与尿素的总质量计)与木质纤维的质量比1∶12,冷冻温度-15℃,冷冻时间45 min;以此工艺活化处理的木质纤维为原料,所制备纤维板的吸水厚度膨胀率、内结合强度、静曲强度、弹性模量分别优于GB/T 11718—2009《中密度纤维板》性能要求(各指标数值分别提升了45%、238%、177%和129%);冷冻活化处理会破坏木质纤维中纤维素间的氢键,提高羟基的反应活性并增加活性羟基的数量,在扩张纤维素晶格的同时产生新的结晶并且降低木质纤维的热稳定性。     

Cu Current Collector with Binder-Free Lithiophilic Nanowire Coating for High Energy Density Lithium Metal Batteries

Despite significant efforts to fabricate high energy density (ED) lithium (Li) metal anodes, problems such as dendrite formation and the need for excess Li (leading to low N/P ratios) have hampered Li metal battery (LMB) development. Here, the use of germanium (Ge) nanowires (NWs) directly grown on copper (Cu) substrates (Cu-Ge) to induce lithiophilicity and subsequently guide Li ions for uniform Li metal deposition/stripping during electrochemical cycling is reported. The NW morphology along with the formation of the Li₁₅Ge₄ phase promotes uniform Li-ion flux and fast charge kinetic, resulting in the Cu-Ge substrate demonstrating low nucleation overpotentials of 10 mV (four times lower than planar Cu) and high Columbic efficiency (CE) efficiency during Li plating/stripping. Within a full-cell configuration, the Cu-Ge@Li – NMC cell delivered a 63.6% weight reduction at the anode level compared to a standard graphite-based anode, with impressive capacity retention and average CE of over 86.5% and 99.2% respectively. The Cu-Ge anodes are also paired with high specific capacity sulfur (S) cathodes, further demonstrating the benefits of developing surface-modified lithiophilic Cu current collectors, which can easily be integrated at the industrial scale.     

Toward an Understanding of Bimetallic MXene Solid-Solution in Binder-Free Electrocatalyst Cathode for Advanced Li–CO2 Batteries

Li–CO₂ batteries have received extensive attention due to their high energy storage capacity and utilization of CO₂ resources. Herein, bimetallic MXene solid-solution TiVC is prepared and combined with highly conductive graphene for the construction of binder-free electrocatalyst cathodes for Li–CO₂ batteries. Considering the electronic structure, the unique synergy effect between Ti and V in TiVC enhances the interfacial chemical bonding ability, facilitates sufficient exposure of active sites and promotes catalytic interfacial structural reformation, thereby promoting the reversible formation and decomposition of the chemically inert discharge product Li₂CO₃. Meanwhile, the abundant pores and excellent electron transfer ability of graphene aerogel are conducive to the gas diffusion and ion transport, thus reducing the mass and charge transfer resistance. As a result, the assembled Li–CO₂ battery presents an excellent discharge capacity of 27 880 mAh g⁻¹ with a stable discharge plateau of 2.77 V and low overpotential of 1.5 V based on the TiVC-graphene aerogel electrocatalytic cathode. The density functional theory calculations are further performed to deeply reveal the unique electronic structure information between Ti and V in the solid-solution TiVC. This study provides inspiration for exploring more bimetallic MXene solid solutions and developing advanced cathode catalysts for flexible Li–CO₂ batteries.     

Ni3V2O8 Nanosheets Grafted on 3D Helical-shaped Carbon Nanocoils as A Binder-free Hierarchical Composite for Efficient Non-enzymatic Glucose Sensing

High fabrication cost, chemical instability, and complex immobilization of enzyme molecules are critical issues of enzyme-based glucose sensors. Designing state-of-the-art, binder-free, and non-enzymatic glucose sensing probes plays an imperative role to cope with the aforementioned issues. 3D carbonaceous nanomaterials coated with transition metal vanadates (TMVs) are a favorable biomimetic platform for glucose quantification. Peculiar hierarchical structure, enhanced conductivity, synergistic interaction, multiple oxidation states, and high catalytic activity would make such composite a potential contender for non-enzymatic glucose sensing. Herein, 3D helical-shaped carbon nanocoils (CNCs) are grown on nickel foam (NF) via chemical vapor deposition method to prepare a robust CNCs/NF scaffold. Then, a hydrothermal route is followed to grow interconnected free-standing Ni₃V₂O₈ nanosheets (NSs) on CNCs/NF scaffold. This novel and binder-free Ni₃V₂O₈ NSs/CNCs/NF hierarchical composite possesses superior electrochemical active area (ECSA) and exceptional electrochemical efficacy. Amperometric analysis exhibits extremely prompt detection time (0.1 s), elevated sensitivity (5214 µA mM⁻¹ cm⁻²), and low detection limit (0.04 µM). Developed sensor demonstrates appreciable recoveries (93.3 to 103.3%) regarding glucose concentration in human serum. The appealing analytical results show that deployment of a 3D helical-shaped hierarchical smart scaffold can be an effective strategy for developing efficient and advanced non-enzymatic glucose sensors.     

Binder-free engineering design of Ni-MOF ultrathin sheet-like grown on PANI@GO decorated nickel foam as an electrode for in hydrogen evolution reaction and asymmetric supercapacitor

In this study, Ni₃(benzene 1,3,5-tricarboxylic acid)@polyaniline-rGO nanocomposite (Ni-MOF@PANI-rGO) is fabricated by a two-step procedure involving polymerization and hydrothermal operations. This nanocomposite-based Ni-MOF was designed for binder-free surface modification of nickel foam (NF). This is offered a novel approach for enhancing the electrochemical performance, and even energy density with a wider operating potential window. An in-situ Ni-MOF was then synthesized on polyaniline@GO (PANI-GO) using an NH-fragment linker and an in-situ hydrothermal technique. The electrochemical behavior of the nanocomposite was studied in asymmetric systems and exhibited outstanding electrochemical performance, high energy density, and power density (73.99 Wh kg⁻¹ at 848.29 W kg⁻¹). The electrode also showed a high specific capacity (1680 C g⁻¹ at 1.0 A g⁻¹) and exceptional cycling stability (92⁒) after 5000 cycles in a three-electrode system. The present results imply a direct application of Ni-MOF@PANI-rGO composite as a bridge performance between supercapacitors and batteries. In addition, the electrocatalyst activity of Ni-MOF@PANI-rGO toward hydrogen evolution reaction (HER) was investigated by linear sweep voltammetry at a scan rate of 10 mV s⁻¹ in 1.0 M KOH. The results showed that Ni-MOF@PAN-rGO acts as a suitable electrocatalyst with the lowest overpotential at 10, 50, and 80 mA cm⁻² and the lowest Tafel slope.