All‐Cellulose‐Based Quasi‐Solid‐State Sodium‐Ion Hybrid Capacitors Enabled by Structural Hierarchy

Na‐ion hybrid capacitors consisting of battery‐type anodes and capacitor‐style cathodes are attracting increasing attention on account of the abundance of sodium‐based resources as well as the potential to bridge the gap between batteries (high energy) and supercapacitors (high power). Herein, hierarchically structured carbon materials inspired by multiscale building units of cellulose from nature are assembled with cellulose‐based gel electrolytes into Na‐ion capacitors. Nonporous hard carbon anodes are obtained through the direct thermal pyrolysis of cellulose nanocrystals. Nitrogen‐doped carbon cathodes with a coral‐like hierarchically porous architecture are prepared via hydrothermal carbonization and activation of cellulose microfibrils. The reversible charge capacity of the anode is 256.9 mAh g^?1 when operating at 0.1 A g^?1 from 0 to 1.5 V versus Na⁺/Na, and the discharge capacitance of cathodes tested within 1.5 to 4.2 V versus Na⁺/Na is 212.4 F g^?1 at 0.1 A g^?1. Utilizing Na⁺ and ClO₄^? as charge carriers, the energy density of the full Na‐ion capacitor with two asymmetric carbon electrodes can reach 181 Wh kg^?1 at 250 W kg^?1, which is one of the highest energy devices reported until now. Combined with macrocellulose‐based gel electrolytes, all‐cellulose‐based quasi‐solid‐state devices are demonstrated possessing additional advantages in terms of overall sustainability.     

High‐Performance Cathode Based on Self‐Templated 3D Porous Microcrystalline Carbon with Improved Anion Adsorption and Intercalation

Dual‐ion batteries (DIBs) have attracted much attention due to their advantages of low cost and especially environmental friendliness. However, the capacities of most DIBs are still unsatisfied (≈100 mAh g^?1) ascribed to the limited capacity of anions intercalation for conventional graphite cathode. In this study, 3D porous microcrystalline carbon (3D‐PMC) was designed and synthesized via a self‐templated growth approach, and when used as cathode for a DIB, it allows both intercalation and adsorption of anions. The microcrystalline carbon is beneficial to obtain capacity originated from anions intercalation, and the 3D porous structure with a certain surface area contributes to anions adsorption capacity. With the synergistic effect, this 3D‐PMC is utilized as cathode and tin as anode for a sodium‐based DIB, which has a high capacity of 168.0 mAh g^?1 at 0.3 A g^?1, among the best values of reported DIBs so far. This cell also exhibits long‐term cycling stability with a capacity retention of ≈70% after 2000 cycles at a high current rate of 1 A g^?1. It is believed that this work will provide a strategy to develop high‐performance cathode materials for DIBs.     

Engineering of Polyanion Type Cathode Materials for Sodium‐Ion Batteries: Toward Higher Energy/Power Density

The development of high energy/power density sodium‐ion batteries (SIBs) is still challenged by the high redox potential of Na/Na⁺ and large radius of Na⁺ ions, thus requiring extensive further improvement to, in particular, enhance the capacity and voltage of cathode materials. Among the various types of cathodes, the polyanion cathodes have emerged as the most pragmatic option due to their outstanding thermostability, unique inductive effect, and flexible structures. In this Review, a critical overview of the design principles and engineering strategies of polyanion cathodes that could have a pivotal role in developing high energy/power density SIBs are presented. Specifically, the engineering of polyanion cathode materials for higher voltage and specific capacity to increase energy density is discussed. The way in which morphology control, architectural design, and electrode processing have been developed to increase power density for SIBs is also analyzed. Finally, the remaining challenges and the future research direction of this field are presented.     

Interlayer Engineering of Molybdenum Trioxide toward High‐Capacity and Stable Sodium Ion Half/Full Batteries

Orthorhombic molybdenum trioxide (MoO₃) is one of the most promising anode materials for sodium‐ion batteries because of its rich chemistry associated with multiple valence states and intriguing layered structure. However, MoO₃ still suffers from the low rate capability and poor cycle induced by pulverization during de/sodiation. An ingenious two‐step synthesis strategy to fine tune the layer structure of MoO₃ targeting stable and fast sodium ionic diffusion channels is reported here. By integrating partially reduction and organic molecule intercalation methodologies, the interlayer spacing of MoO₃ is remarkably enlarged to 10.40 Å and the layer structural integration are reinforced by dimercapto groups of bismuththiol molecules. Comprehensive characterizations and density functional theory calculations prove that the intercalated bismuththiol (DMcT) molecules substantially enhanced electronic conductivity and effectively shield the electrostatic interaction between Na⁺ and the MoO₃ host by conjugated double bond, resulting in improved Na⁺ insertion/extraction kinetics. Benefiting from these features, the newly devised layered MoO₃ electrode achieves excellent long‐term cycling stability and outstanding rate performance. These achievements are of vital significance for the preparation of sodium‐ion battery anode materials with high‐rate capability and long cycling life using intercalation chemistry.     

Oxygen Vacancies Evoked Blue TiO2(B) Nanobelts with Efficiency Enhancement in Sodium Storage Behaviors

Oxygen vacancies (OVs) dominate the physical and chemical properties of metal oxides, which play crucial roles in the various fields of applications. Density functional theory calculations show the introduction of OVs in TiO₂(B) gives rise to better electrical conductivity and lower energy barrier of sodiation. Here, OVs evoked blue TiO₂(B) (termed as B‐TiO₂(B)) nanobelts are successfully designed upon the basis of electronically coupled conductive polymers to TiO₂, which is confirmed by electron paramagnetic resonance and X‐ray photoelectron spectroscopy. The superiorities of OVs with the aid of carbon encapsulation lead to higher capacity (210.5 mAh g^?1 (B‐TiO₂(B)) vs 102.7 mAh g^?1 (W‐TiO₂(B)) at 0.5 C) and remarkable long‐term cyclability (the retention of 94.4% at a high rate of 10 C after 5000 times). In situ X‐ray diffractometer analysis spectra also confirm that an enlarged interlayer spacing stimulated by OVs is beneficial to accommodate insertion and removal of sodium ions to accelerate storage kinetics and preserve its original crystal structure. The work highlights that injecting OVs into metal oxides along with carbon coating is an effective strategy for improving capacity and cyclability performances in other metal oxide based electrochemical energy systems.     

A Structurable Gel‐Polymer Electrolyte for Sodium Ion Batteries

In this work, a structurable gel‐polymer electrolyte (SGPE) with a controllable pore structure that is not destroyed after immersion in an electrolyte is produced via a simple nonsolvent induced phase separation (NIPS) method. This study investigates how the regulation of the nonsolvent content affects the evolving nanomorphology of the composite separators and overcomes the drawbacks of conventional separators, such as glass fiber (GF), which has been widely used in sodium ion batteries (SIBs), through the regulation of pore size and gel‐polymer position. The interfacial resistance is reduced through selective positioning of a poly(vinylidene fluoride‐co‐hexa fluoropropylene) (PVdF‐HFP) gel‐polymer with the aid of NIPS, which in turn enhances the compatibility between the electrolyte and electrode. In addition, the highly porous morphology of the GF/SGPE obtained via NIPS allows for the absorption of more liquid electrolyte. Thus, a greatly improved cell performance of the SIBs is observed when a tailored SGPE is incorporated into the GF separator through charge/discharge testing compared with the performance observed with pristine GF and conventional GF coated with PVdF‐HFP gel‐polymer.     

General Synthesis of Dual Carbon‐Confined Metal Sulfides Quantum Dots Toward High‐Performance Anodes for Sodium‐Ion Batteries

Sponge‐like composites assembled by cobalt sulfides quantum dots (Co₉S₈ QD), mesoporous hollow carbon polyhedral (HCP) matrix, and a reduced graphene oxide (rGO) wrapping sheets are synthesized by a simultaneous thermal reduction, carbonization, and sulfidation of zeolitic imidazolate frameworks@GO precursors. Specifically, Co₉S₈ QD with size less than 4 nm are homogenously embedded within HCP matrix, which is encapsulated in macroporous rGO, thereby leading to the double carbon‐confined hierarchical composites with strong coupling effect. Experimental data combined with density functional theory calculations reveal that the presence of coupled rGO not only prevents the aggregation and excessive growth of particles, but also expands the lattice parameters of Co₉S₈ crystals, enhancing the reactivity for sodium storage. Benefiting from the hierarchical porosity, conductive network, structural integrity, and a synergistic effect of the components, the sponge‐like composites used as binder‐free anodes manifest outstanding sodium‐storage performance in terms of excellent stable capacity (628 mAh g^?1 after 500 cycles at 300 mA g^?1) and exceptional rate capability (529, 448, and 330 mAh g^?1 at 1600, 3200, and 6400 mA g^?1). More importantly, the synthetic method is very versatile and can be easily extended to fabricate other transition‐metal‐sulfides‐based sponge‐like composites with excellent electrochemical performances.     

组合捕收剂对某石英型萤石矿的浮选试验研究（增刊）

江西某石英型萤石矿,其中大部分萤石与石英紧密连生,造成单体解离困难,从而影响矿物选别指标。化学多元素分析结果表明,矿石中CaF2品位为67.86%,SiO2、CaO、Al2O3含量较高,分别为19.04%、5.91%和3.32%。这表明矿石中脉石以石英和硅酸盐矿物为主,其他成分含量较少。本文探究了油酸钠（NaOl）和叔十二烷基硫醇（TDM）组合捕收剂对该石英型萤石矿的浮选效果,并对捕收剂进行了表面张力测定。浮选结果表明,组合捕收剂在矿浆pH为9.5,油酸钠和叔十二烷基硫醇摩尔比为8:2时,对萤石的浮选指标最好,通过1粗4精3扫全闭路浮选流程可获得CaF2品位为94.06%,回收率为99.55%的高品级萤石精矿。捕收剂的表面张力测试表明,组合捕收剂的CMC值略小于油酸钠,且在气—液界面的分子排列紧密度高于油酸钠。因此,相比于油酸钠来说,组合捕收剂可以更好的改变矿物表面的疏水能力。上述研究成果可为嵌布粒度细的石英型萤石矿的有效回收利用提供技术支持。     

钠过量对铌酸钾钠基陶瓷结构及性能的影响

用常规氧化物固溶法制备了(Na0.520+xK0.480)0.915Li0.085NbO3(x=0～0.025)无铅压电陶瓷,研究了过量Na的掺杂量对其烧结温度、微观结构及压电性能的影响。结果表明,过量Na掺杂在烧结过程中促进液相的产生,导致样品烧结温度显著降低。室温下样品均为四方结构。随x的增加,样品的斜方-四方相变温度tO-T趋向低温。当x从0.010增大到0.025时,Qm从131提高到238,tanδ和d33分别从0.034和125pC/N下降至0.012和105pC/N,表明过量Na实际上起到了"硬性掺杂"的作用。     

(Na_(1/2)Bi_(1/2))TiO_3-SrTiO_3无铅压电陶瓷的介电、压电性能

研究了 (Na1 / 2 Bi1 / 2 ) Ti O3- Sr Ti O3二元系无铅压电陶瓷的介电、压电性性。Sr2 的引入对 NBT材料的常温介电系数、铁电相与反铁电相转变温度 TF A(180°C)以及居里温度 TC(30 0°C)的影响都不大 ,但却较大幅度地降低了 NBT材料的高矫顽场 ,从而使极化相对容易。(Na1 / 2 Bi1 / 2 ) Ti O3- Sr Ti O3二元系的压电性能参数 d33和 kt分别达到 10 0 p C/N和 0 .45