中国科学院成功研制出氧化钛“光开关”材料

采用循环伏安电沉积技术在钛基上获得水合氧化钌(RuOx·nH2O),其比容量为105F/g。通过电化学测试(循环伏安、恒电流充放电)、X射线衍射(XRD)、扫描电镜(SEM)以及X射线光电子能谱(XPS)等方法研究了沉积物的电化学性质、物相及组成。结果表明:电沉积法获得的水合氧化钌呈非晶态结构,它由多氧化态钌混合羟基氧化物组成。在1.0mol·L-1H2SO4溶液中,该氧化物呈准电容特征,有较高电化学可逆性,可用作电化学电容器电极材料。     

Intercalative Motifs-Induced Space Confinement and Bonding Covalency Enhancement Enable Ultrafast and Large Sodium Storage

Alloying-type metal sulfides with high theoretical capacities are promising anodes for sodium-ion batteries, but suffer from sluggish sodiation kinetics and huge volume expansion. Introducing intercalative motifs into alloying-type metal sulfides is an efficient strategy to solve the above issues. Herein, robust intercalative In S motifs are grafted to high-capacity layered Bi₂S₃ to form a cation-disordered (BiIn)₂S₃, synergistically realizing high-rate and large-capacity sodium storage. The In S motif with strong bonding serves as a space-confinement unit to buffer the volume expansion, maintaining superior structural stability. Moreover, the grafted high-metallicity Indium increases the bonding covalency of Bi S, realizing controllable reconstruction of Bi S bond during cycling to effectively prevent the migration and aggregation of atomic Bi. The novel (BiIn)₂S₃ anode delivers a high capacity of 537 mAh g⁻¹ at 0.4 C and a superior high-rate stability of 247 mAh g⁻¹ at 40 C over 10000 cycles. Further in situ and ex situ characterizations reveal the in-depth reaction mechanism and the breakage and formation of reversible Bi S bonds. The proposed space confinement and bonding covalency enhancement strategy via grafting intercalative motifs can be conducive to developing novel high-rate and large-capacity anodes.     

Unraveling the Charge Storage and Activity-Enhancing Mechanisms of Zn-Doping Perovskite Fluorides and Engineering the Electrodes and Electrolytes for Wide-Temperature Aqueous Supercabatteries

Herein, a trimetallic Ni–Co–Zn perovskite fluoride (ABF₃) (denoted as KNCZF) electrode material is explored for advanced aqueous supercabatteries (ASCBs), with KNCZF and activated carbon–FeBiCu@reduced graphene oxides (AC–FeBiCu@rGO) as cathode and anode, respectively, which outperform aqueous supercapacitors (ASCs) and batteries (ABs) with AC and FeBiCu@rGO anodes because of the synergistic effect of pseudocapacitive (KNCZF), capacitive (AC), and faradaic (FeBiCu@rGO) responses. One of the important findings is that the KNCZF shows a typical bulk phase conversion mechanism for charge storage in the alkaline media with the transition of ABF₃ perovskite nanocrystals into amorphous metal oxides/(oxy)hydroxides nanosheets, showing the redox-active and redox-inert roles for the Ni/Co and Zn species, respectively, which can be deduced by various ex-situ techniques. Another interesting finding is that the redox-inert Zn species largely enhance the activity of Ni/Co redox-active species in the ABF₃ materials, mainly owing to the promotion of surface electroactive sites, adsorption of OH^?, and charge transfer of surface Ni/Co atoms by Zn-doping, which can be proved by ex-situ characterizations and theoretical calculations. Overall, this study reveals the structure–activity relationship and charge storage mechanisms of Zn-doping ABF₃ materials for advanced ASCBs, showing a great impact on developing advanced electrochemical energy storage.     

Mesoporous NiS2 Nanospheres Anode with Pseudocapacitance for High‐Rate and Long‐Life Sodium‐Ion Battery

It is of great importance to exploit electrode materials for sodium‐ion batteries (SIBs) with low cost, long life, and high‐rate capability. However, achieving quick charge and high power density is still a major challenge for most SIBs electrodes because of the sluggish sodiation kinetics. Herein, uniform and mesoporous NiS₂ nanospheres are synthesized via a facile one‐step polyvinylpyrrolidone assisted method. By controlling the voltage window, the mesoporous NiS₂ nanospheres present excellent electrochemical performance in SIBs. It delivers a high reversible specific capacity of 692 mA h g^?1. The NiS₂ anode also exhibits excellent high‐rate capability (253 mA h g^?1 at 5 A g^?1) and long‐term cycling performance (319 mA h g^?1 capacity remained even after 1000 cycles at 0.5 A g^?1). A dominant pseudocapacitance contribution is identified and verified by kinetics analysis. In addition, the amorphization and conversion reactions during the electrochemical process of the mesoporous NiS₂ nanospheres is also investigated by in situ X‐ray diffraction. The impressive electrochemical performance reveals that the NiS₂ offers great potential toward the development of next generation large scale energy storage.     

Pseudocapacitive Sodium Storage by Ferroelectric Sn2P2S6 with Layered Nanostructure

Sodium ion batteries (SIB) are considered promising alternative candidates for lithium ion batteries (LIB) because of the wide availability and low cost of sodium, therefore the development of alternative sodium storage materials with comparable performance to LIB is urgently desired. The sodium ions with larger sizes resist intercalation or alloying because of slow reaction kinetics. Most pseudocapacitive sodium storage materials are based on subtle nanomaterial engineering, which is difficult for large‐scale production. Here, ferroelectric Sn₂P₂S₆ with layered nanostructure is developed as sodium ion storage material. The ferroelectricity‐enhanced pseudocapacitance of sodium ion in the interlayer spacing makes the electrochemical reaction easier and faster, endowing the Sn₂P₂S₆ electrode with excellent rate capability and cycle stability. Furthermore, the facile solid state reaction synthesis and common electrode fabrication make the Sn₂P₂S₆ that becomes a promising anode material of SIB.     

超级电容器用活性炭电极表面氧化改性后的电化学性能

以椰壳活性炭和杏壳活性炭为原料,采用浓硝酸液相氧化改性处理后,制成以 KOH 为电解液的超级电容器的炭电极。采用低温 N_2吸附法表征了活性炭的孔结构性质,并采用循环伏安法和交流阻抗法考察了活性炭电极的电化学性能。实验表明,经浓硝酸氧化处理后,活性炭的比表面积和孔容降低,平均孔径增大。但由于氧化处理后材料赝电容的增加,椰壳活性炭和杏壳活性炭的放电容量不但没有降低.反由原来的114 F·g~(-1)和98 F·g~(-1)分别增大到166 F·g~(-1)和157 F·g~(-1)。同时,浓硝酸氧化降低了活性炭电极的表面电荷迁移电阻和时间常数。     

基于赝电容的高线性度柔性压力传感器研究

基于可逆氧化还原反应的赝电容式柔性压力传感器具备高灵敏性能,可用于微弱压力检测,然而,目前赝电容式柔性压 力传感器线性度较差,只能在有限压力区间内保持较高灵敏度。 为此,本文利用 MXene 材料作为电极,设计了一种内部具有孔 隙且表面粗糙的双尺度随机微结构离子凝胶膜,增加了其压缩过程中的缓冲空间,使凝胶膜应力变形更加均匀,确保了灵敏度 在受压过程中保持稳定。 实验数据表明,传感器在 0 ~ 1 MPa 范围内具有超高的线性度(相关系数 ~ 0. 994),优异的灵敏度 ( ~ 2 133. 7 kPa -1 )、快速的响应和恢复时间(分别为~15 和~23 ms),较低的检测限( ~ 2. 5 Pa)和优异的机械稳定性。 将传感器 用于水下,可高线性检测水深,同时传感器可以高灵敏检测到不同水深下螺旋桨扰动产生的微弱水流变化。     

Improved capacitance characteristics during electrochemical charging of carbon nanotubes modified with polyoxometallate monolayers

By modification of surfaces of multi-walled carbon nanotubes with ultra-thin monolayer-type films of phosphododecamolybdic acid, H₃PMo₁₂O₄₀, an electrode material with improved capacitance properties is produced. It is apparent from three distinct test experiments (based on cyclic voltammetry, galavanostatic charging-discharging and AC impedance) that capacitors utilizing H₃PMo₁₂O₄₀-modified carbon nanotubes are characterized by specific capacitances and energy densities on the levels of 40 F g⁻¹ and 1.3 Wh kg⁻¹, whereas the respective values for the systems built from bare carbon nanotubes are lower, 22 F g⁻¹ and 0.7 Wh kg⁻¹. It is reasonable to expect that fast and reversible multi-electron transfers of the Keggin-type H₃PMo₁₂O₄₀ account for the pseudocapacitance effect and significantly contribute to the observed overall capacitance.     

SnO2/介孔炭复合材料的电容性能

以介孔炭(MC)、锡粉和浓HCl为原料,采用MC浸渍SnCl2溶液,煅烧制得SnO2/MC复合材料,并测试了电容性能。TEM、XRD、EDS和N2吸附-脱附曲线分析发现:生成的SnO2负载到了MC的表面和孔道中。复合材料具有典型的电容特性,与1.0 mol/L NaOH构成电容器单元,在-0.8~0.2 V以1 mA充放电,比电容最高达274 F/g。