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.     

A General Strategy for Antimony-Based Alloy Nanocomposite Embedded in Swiss-Cheese-Like Nitrogen-Doped Porous Carbon for Energy Storage

Due to its suitable working voltage and high theoretical storage capacity, antimony is considered a promising negative electrode material for lithium-ion batteries (LIBs) and has attracted widespread attention. The volume effect during cycling, however, will cause the antimony anode to undergo a severe structural collapse and a rapid decrease in capacity. Here, a general in situ self-template-assisted strategy is proposed for the rational design and preparation of a series of M Sb (M = Ni, Co, or Fe) nanocomposites with M N C coordination, which are firmly anchored on Swiss-cheese-like nitrogen-doped porous carbon as anodes for LIBs. The large interface pore network structure, the introduction of heteroatoms, and the formation of strong metal N C bonds effectively enhance their electronic conductivity and structural integrity, and provide abundant interfacial lithium storage. The experimental results have proved the high rate performance and excellent cycling stability of antimony-based composite materials. Electrochemical kinetics studies have demonstrated that the increase in capacity during cycling is mainly controlled by the diffusion mechanism rather than the pseudocapacitance contribution. This facile strategy can provide a new pathway for low-cost and high-yield synthesis of Sb-based composites with high performance, and is expected to be applied in other energy-related fields such as sodium-/potassium-ion batteries or electrocatalysis.     

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.     

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。     

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。     

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.     

Coupling PEDOT on Mesoporous Vanadium Nitride Arrays for Advanced Flexible All‐Solid‐State Supercapacitors

Tailored construction of advanced flexible supercapacitors (SCs) is of great importance to the development of high‐performance wearable modern electronics. Herein, a facile combined wet chemical method to fabricate novel mesoporous vanadium nitride (VN) composite arrays coupled with poly(3,4‐ethylenedioxythiophene) (PEDOT) as flexible electrodes for all‐solid‐state SCs is reported. The mesoporous VN nanosheets arrays prepared by the hydrothermal–nitridation method are composed of cross‐linked nanoparticles of 10–50 nm. To enhance electrochemical stability, the VN is further coupled with electrodeposited PEDOT shell to form high‐quality VN/PEDOT flexible arrays. Benefiting from high intrinsic reactivity and enhanced structural stability, the designed VN/PEDOT flexible arrays exhibit a high specific capacitance of 226.2 F g^?1 at 1 A g^?1 and an excellent cycle stability with 91.5% capacity retention after 5000 cycles at 10 A g^?1. In addition, high energy/power density (48.36 Wh kg^?1 at 2 A g^?1 and 4 kW kg^?1 at 5 A g^?1) and notable cycling life (91.6% retention over 10 000 cycles) are also achieved in the assembled asymmetric flexible supercapacitor cell with commercial nickel–cobalt–aluminum ternary oxides cathode and VN/PEDOT anode. This research opens up a way for construction of advanced hybrid organic–inorganic electrodes for flexible energy storage.     

Tailoring 2D Heteroatom‐Doped Carbon Nanosheets with Dominated Pseudocapacitive Behaviors Enabling Fast and High‐Performance Sodium Storage

2D carbon nanosheets are considered to be promising candidates for use as sodium ion battery (SIB) anodes due to their large specific surface area and excellent electronic conductivity. However, their applications are hampered by inferior cycling performance, insufficient storage capacity, and high cost. N, B co‐doping carbon nanosheets (NBTs) are synthesized using biomass‐based gelatin as carbon precursor and boric acid as template, and demonstrate their great potential as high‐performance SIB anodes in practical applications. The synergistic effect of heteroatom doping and ultrathin 2D structure provides the NBTs with abundant defects, active sites, and short ion/electron transfer distance, which favors and improves the storage capabilities and rate performances. The optimized NBTs present a remarkable cyclability and superb rate capability (309 mAh g^?1 at 0.2 A g^?1 for 200 cycles; 225 mAh g^?1 at 1 A g^?1 for 2000 cycles). Meanwhile, the Na storage mechanism is proved to be a pseudocapacitive‐controlled process, which accounts for the fast charge/discharge behaviors. This work demonstrates an effective template method to produce 2D heteroatoms co‐doping carbon nanosheets to achieve excellent Na storage performances.     

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。     

Ru_(0.1)Mn_(0.9)O_x的制备与电化学赝电容特性研究

结合氧化钌理想的电化学赝电容特性和二氧化锰资源广泛、对环境友好的优势,采用氧化共沉淀法制备出Ru0.1Mn0.9Ox新型电化学电容器复合电极材料,通过循环伏安(CV)、计时电位(Chronopotentiometry)、交流阻抗(AC impedance)、热重-差热(TG/DSC)以及X射线衍射(XRD)等实验研究了电极材料的电化学赝电容性、阻抗特征、晶形结构及热处理温度对材料的晶形和赝电容的影响.结果表明:当热处理温度低于180 ℃时,可制备出稳定、非晶态的Ru0.1Mn0.9Ox;当温度为350 ℃时,复合材料中的无定形二氧化锰已转变为α-MnO2,掺杂的氧化钌晶形不变.与纯MnO2相比,Ru0.1Mn0.9Ox复合电极材料具有较低的极化内阻、较高的比电容、良好的电化学可逆性和显著的电化学赝电容特征.