表面活性剂对NiCo2S4纳米薄膜的电化学性能影响的研究

通过水热法在泡沫镍上成功制备了纳米结构的NiCo₂S₄薄膜, 主要包括前驱体制备及硫化过程。研究表明, 制备过程中添加不同种类的表面活性剂会对NiCo₂S₄薄膜的形貌、结构和电化学性能产生影响。添加表面活性剂后, NiCo₂S₄会自组装逐渐形成三维纳米片网状结构。在所有的NiCo₂S₄薄膜中, 添加SDS表面活性剂的薄膜表现出最高的比电容(在0.5 A/g电流密度下达到2893 F/g)、出色的倍率特性(在10 A/g电流密度下达到1890.6 F/g)和良好的循环稳定性(1000次循环后保持率为96.1%)。研究结果表明纳米网状的NiCo₂S₄是一种极具潜力的超级电容器电极材料。     

Hierarchical 3D Cobalt‐Doped Fe3O4 Nanospheres@NG Hybrid as an Advanced Anode Material for High‐Performance Asymmetric Supercapacitors

Hierarchical nanostructure, high electrical conductivity, extraordinary specific surface area, and unique porous architecture are essential properties in energy storage and conversion studies. A new type of hierarchical 3D cobalt encapsulated Fe₃O₄ nanosphere is successfully developed on N‐graphene sheet (Co?Fe₃O₄ NS@NG) hybrid with unique nanostructure by simple, scalable, and efficient solvothermal technique. When applied as an electrode material for supercapacitors, hierarchical Co?Fe₃O₄ NS@NG hybrid shows an ultrahigh specific capacitance (775 F g^?1 at a current density of 1 A g^?1) with exceptional rate capability (475 F g^?1 at current density of 50 A g^?1), and admirable cycling performance (97.1% capacitance retention after 10 000 cycles). Furthermore, the fabricated Co?Fe₃O₄ NS@NG//CoMnO₃@NG asymmetric supercapacitor (ASC) device exhibits a high energy density of 89.1 Wh kg^?1 at power density of 0.901 kW kg^?1, and outstanding cycling performance (89.3% capacitance retention after 10 000 cycles). Such eminent electrochemical properties of the Co?Fe₃O₄ NS@NG are due to the high electrical conductivity, ultrahigh surface area, and unique porous architecture. This research first proposes hierarchical Co?Fe₃O₄ NS@NG hybrid as an ultrafast charge?discharge anode material for the ASC device, that holds great potential for the development of high‐performance energy storage devices.     

Liquid‐Alloy‐Assisted Growth of 2D Ternary Ga2In4S9 toward High‐Performance UV Photodetection

2D ternary systems provide another degree of freedom of tuning physical properties through stoichiometry variation. However, the controllable growth of 2D ternary materials remains a huge challenge that hinders their practical applications. Here, for the first time, by using a gallium/indium liquid alloy as the precursor, the synthesis of high‐quality 2D ternary Ga₂In₄S₉ flakes of only a few atomic layers thick (≈2.4 nm for the thinnest samples) through chemical vapor deposition is realized. Their UV‐light‐sensing applications are explored systematically. Photodetectors based on the Ga₂In₄S₉ flakes display outstanding UV detection ability (R _λ = 111.9 A W^?1, external quantum efficiency = 3.85 × 10⁴%, and D* = 2.25 × 10¹¹ Jones@360 nm) with a fast response speed (τ_ring ≈ 40 ms and τ_decay ≈ 50 ms). In addition, Ga₂In₄S₉‐based phototransistors exhibit a responsivity of ≈10⁴ A W^?1@360 nm above the critical back‐gate bias of ≈0 V. The use of the liquid alloy for synthesizing ultrathin 2D Ga₂In₄S₉ nanostructures may offer great opportunities for designing novel 2D optoelectronic materials to achieve optimal device performance.     

Engineering 2D Architectures toward High‐Performance Micro‐Supercapacitors

The rise of micro‐supercapacitors is satisfying the demand for power storage in portable devices and wireless gadgets. But the miniaturization of the energy‐storage components is significantly limited by their energy density. Electrode materials with adequate electrochemical active surfaces are therefore required for improving performance. 2D materials with ultralarge specific surface areas offer a broad portfolio of the development of high‐performance micro‐supercapacitors in spite of their several critical drawbacks. An architecture engineering strategy is therefore developed to break these natural limits and maximize the significant advantages of these materials. Based on the approaches of phase transformation, intercalation, surface modification, material hybridization, and hierarchical structuration, 2D architectures with improved conductivity, enlarged specific surface, enhanced redox activity, as well as the unique synergetic effect exhibit great promise in the application of miniaturized supercapacitors with highly enhanced performance. Herein, the architecture engineering of emerging 2D materials beyond graphene toward optimizing the performance of micro‐supercapacitors is discussed, in order to promote the application of 2D architectures in miniaturized energy‐storage devices.     

Electrolyte Engineering on Performance Enhancement of NiCo2S4 Anode for Sodium Storage

NiCo₂S₄ is an attractive anode for sodium-ion batteries (SIBs) due to its high capacity and excellent redox reversibility. Practical deployment of NiCo₂S₄ electrode in SIBs, however, is still hindered by the inferior capacity and unsatisfactory cycling performance, which result from the mismatch between the electrolyte chemistry and electrode. Herein, a functional electrolyte containing 1.0 m NaCF₃SO₃ in diethylene glycol dimethyl ether (DEGDME) (1.0 m NaCF₃SO₃-DEGDME) is developed, which can be readily used for NiCo₂S₄ anode with high initial coulomb efficiency (96.2%), enhanced cycling performance, and boosted capacities (341.7 mA h g⁻¹ after 250 continuous cycles at the current density of 200 mA g⁻¹). The electrochemical tests and related phase characterization combined with density functional theory (DFT) calculation indicate the ether-based electrolyte is more suitable for the NiCo₂S₄ anode in SIBs due to the formation of a stable electrode–electrolyte interface. Additionally, the importance of the voltage window is also demonstrated to further optimize the electrochemical performance of the NiCo₂S₄ electrode. The formation of sulfide intermediates during charging and discharging is predicted by combining DFT and verified by in situ XRD and HRTEM. The findings indicate that electrolyte engineering would be an effective way of performance enhancement for sulfides in practical SIBs.     

One‐Pot Synthesis of Tunable Crystalline Ni3S4@Amorphous MoS2 Core/Shell Nanospheres for High‐Performance Supercapacitors

Transition metal sulfides gain much attention as electrode materials for supercapacitors due to their rich redox chemistry and high electrical conductivity. Designing hierarchical nanostructures is an efficient approach to fully utilize merits of each component. In this work, amorphous MoS₂ is firstly demonstrated to show specific capacitance 1.6 times as that of the crystalline counterpart. Then, crystalline core@amorphous shell (Ni₃S₄@MoS₂) is prepared by a facile one‐pot process. The diameter of the core and the thickness of the shell can be independently tuned. Taking advantages of flexible protection of amorphous shell and high capacitance of the conductive core, Ni₃S₄@amorphous MoS₂ nanospheres are tested as supercapacitor electrodes, which exhibit high specific capacitance of 1440.9 F g^?1 at 2 A g^?1 and a good capacitance retention of 90.7% after 3000 cycles at 10 A g^?1. This design of crystalline core@amorphous shell architecture may open up new strategies for synthesizing promising electrode materials for supercapacitors.     

High‐Performance 2.6 V Aqueous Asymmetric Supercapacitors based on In Situ Formed Na0.5MnO2 Nanosheet Assembled Nanowall Arrays

The voltage limit for aqueous asymmetric supercapacitors is usually 2 V, which impedes further improvement in energy density. Here, high Na content Birnessite Na_0.5MnO₂ nanosheet assembled nanowall arrays are in situ formed on carbon cloth via electrochemical oxidation. It is interesting to find that the electrode potential window for Na_0.5MnO₂ nanowall arrays can be extended to 0–1.3 V (vs Ag/AgCl) with significantly increased specific capacitance up to 366 F g^?1. The extended potential window for the Na_0.5MnO₂ electrode provides the opportunity to further increase the cell voltage of aqueous asymmetric supercapacitors beyond 2 V. To construct the asymmetric supercapacitor, carbon‐coated Fe₃O₄ nanorod arrays are synthesized as the anode and can stably work in a negative potential window of ?1.3 to 0 V (vs Ag/AgCl). For the first time, a 2.6 V aqueous asymmetric supercapacitor is demonstrated by using Na_0.5MnO₂ nanowall arrays as the cathode and carbon‐coated Fe₃O₄ nanorod arrays as the anode. In particular, the 2.6 V Na_0.5MnO₂//Fe₃O₄@C asymmetric supercapacitor exhibits a large energy density of up to 81 Wh kg^?1 as well as excellent rate capability and cycle performance, outperforming previously reported MnO₂‐based supercapacitors. This work provides new opportunities for developing high‐voltage aqueous asymmetric supercapacitors with further increased energy density.     

Fabrication of a 3D Hierarchical Sandwich Co9S8/α‐MnS@N–C@MoS2 Nanowire Architectures as Advanced Electrode Material for High Performance Hybrid Supercapacitors

Supercapacitors suffer from lack of energy density and impulse the energy density limit, so a new class of hybrid electrode materials with promising architectures is strongly desirable. Here, the rational design of a 3D hierarchical sandwich Co₉S₈/α‐MnS@N–C@MoS₂ nanowire architecture is achieved during the hydrothermal sulphurization reaction by the conversion of binary mesoporous metal oxide core to corresponding individual metal sulphides core along with the formation of outer metal sulphide shell at the same time. Benefiting from the 3D hierarchical sandwich architecture, Co₉S₈/α‐MnS@N–C@MoS₂ electrode exhibits enhanced electrochemical performance with high specific capacity/capacitance of 306 mA h g^?1/1938 F g^?1 at 1 A g^?1, and excellent cycling stability with a specific capacity retention of 86.9% after 10 000 cycles at 10 A g^?1. Moreover, the fabricated asymmetric supercapacitor device using Co₉S₈/α‐MnS@N–C@MoS₂ as the positive electrode and nitrogen doped graphene as the negative electrode demonstrates high energy density of 64.2 Wh kg^?1 at 729.2 W kg^?1, and a promising energy density of 23.5 Wh kg^?1 is still attained at a high power density of 11 300 W kg^?1. The hybrid electrode with 3D hierarchical sandwich architecture promotes enhanced energy density with excellent cyclic stability for energy storage.     

(Ni,Co)Se2/NiCo‐LDH Core/Shell Structural Electrode with the Cactus‐Like (Ni,Co)Se2 Core for Asymmetric Supercapacitors

Supercapacitors (SCs) have been widely studied as a class of promising energy‐storage systems for powering next‐generation E‐vehicles and wearable electronics. Fabricating hybrid‐types of electrode materials and designing smart nanoarchitectures are effective approaches to developing high‐performance SCs. Herein, first, a Ni‐Co selenide material (Ni,Co)Se₂ with special cactus‐like structure as the core, to scaffold the NiCo‐layered double hydroxides (LDHs) shell, is designed and fabricated. The cactus‐like structural (Ni,Co)Se₂ core, as a highly conductive and robust support, promotes the electron transport as well as hinders the agglomeration of LDHs. The synergistic contributions from the two types of active materials together with the superior properties of the cactus‐like nanostructure enable the (Ni,Co)Se₂/NiCo‐LDH hybrid electrode to exhibit a high capacity of ≈170 mA h g^?1 (≈1224 F g^?1), good rate performance, and long durability. The as‐assembled (Ni,Co)Se₂/NiCo‐LDH//PC (porous carbon) asymmetric supercapacitor (ASC) with an operating voltage of 1.65 V delivers a high energy density of 39 W h kg^?1 at a power density of 1650 W kg^?1. Therefore, the cactus‐like core/shell structure offers an effective pathway to engineer advanced electrodes. The assembled flexible ASC is demonstrated to effectively power electronic devices.     

Large‐Area,Uniform, Aligned Arrays of Na3(VO)2(PO4)2F on Carbon Nanofiber for Quasi‐Solid‐State Sodium‐Ion Hybrid Capacitors

Sodium–vanadium fluorophosphate (Na₃V₂O_2x(PO₄)₂F_3?2x, NVPF, 0 ≤ x ≤ 1) is considered to be a promising Na‐storage cathode material due to its high operation potentials (3.6–4 V) and minor volume variation (1.8%) during Na⁺‐intercalation. Research about NVPF is mainly focused on powder‐type samples, while its ordered array architecture is rarely reported. In this work, large‐area and uniform Na₃(VO)₂(PO₄)₂F cuboid arrays are vertically grown on carbon nanofiber (CNF) substrates for the first time. Owing to faster electron/ion transport and larger electrolyte–electrode contact area, the as‐prepared NVPF array electrode exhibits much improved Na‐storage properties compared to its powder counterpart. Importantly, a quasi‐solid‐state sodium‐ion hybrid capacitor (SIHC) is constructed based on the NVPF array as an intercalative battery cathode and porous CNF as a capacitive supercapacitor anode together with the P(VDF‐HFP)‐based polymer electrolyte. This novel hybrid system delivers an attractive energy density of ≈227 W h kg^?1 (based on total mass of two electrodes), and still remains as high as 107 Wh kg^?1 at a high specific power of 4936 W kg^?1, which pushes the energy output of sodium hybrid capacitors toward a new limit. In addition, the growth mechanism of NVPF arrays is investigated in detail.     

Coordination‐Driven Hierarchical Assembly of Hybrid Nanostructures Based on 2D Materials

2D materials have received tremendous scientific and engineering interests due to their remarkable properties and broad‐ranging applications such as energy storage and conversion, catalysis, biomedicine, electronics, and so forth. To further enhance their performance and endow them with new functions, 2D materials are proposed to hybridize with other nanostructured building blocks, resulting in hybrid nanostructures with various morphologies and structures. The properties and functions of these hybrid nanostructures depend strongly on the interfacial interactions between 2D materials and other building blocks. Covalent and coordination bonds are two strong interactions that hold high potential in constructing these robust hybrid nanostructures based on 2D materials. However, most 2D materials are chemically inert, posing problems for the covalent assembly with other building blocks. There are usually coordination atoms in most of 2D materials and their derivatives, thus coordination interaction as a strong interfacial interaction has attracted much attention. In this review, recent progress on the coordination‐driven hierarchical assembly based on 2D materials is summarized, focusing on the synthesis approaches, various architectures, and structure–property relationship. Furthermore, insights into the present challenges and future research directions are also presented.     

Defect‐Enriched Nitrogen Doped–Graphene Quantum Dots Engineered NiCo2S4 Nanoarray as High‐Efficiency Bifunctional Catalyst for Flexible Zn‐Air Battery

Flexible Zn‐air batteries have recently emerged as one of the key energy storage systems of wearable/portable electronic devices, drawing enormous attention due to the high theoretical energy density, flat working voltage, low cost, and excellent safety. However, the majority of the previously reported flexible Zn‐air batteries encounter problems such as sluggish oxygen reaction kinetics, inferior long‐term durability, and poor flexibility induced by the rigid nature of the air cathode, all of which severely hinder their practical applications. Herein, a defect‐enriched nitrogen doped–graphene quantum dots (N‐GQDs) engineered 3D NiCo₂S₄ nanoarray is developed by a facile chemical sulfuration and subsequent electrophoretic deposition process. The as‐fabricated N‐GQDs/NiCo₂S₄ nanoarray grown on carbon cloth as a flexible air cathode exhibits superior electrocatalytic activities toward both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), outstanding cycle stability (200 h at 20 mA cm^?2), and excellent mechanical flexibility (without observable decay under various bending angles). These impressive enhancements in electrocatalytic performance are mainly attributed to bifunctional active sites within the N‐GQDs/NiCo₂S₄ catalyst and synergistic coupling effects between N‐GQDs and NiCo₂S₄. Density functional theory analysis further reveals that stronger OOH* dissociation adsorption at the interface between N‐GQDs and NiCo₂S₄ lowers the overpotential of both ORR and OER.     

“一步法”合成NiCo_2S_4纳米阵列高性能能量存储器件电极的研究

通过简单的"一步低温原位合成"法成功制备出了以泡沫镍为基底的具有自支撑结构的分层三维网络的NiCo_2S_4纳米阵列,采用SEM、XRD对产物的微观结构进行表征,并对其进行电化学性能测试。结果表明,由于这种独特的分层网络结构,该NiCo_2S_4纳米阵列不仅能够为能量存储提供大量的电化学活性位点,而且拥有良好的电子传递性能,NiCo_2S_4@泡沫镍电极在20 m A/cm~2的电流密度下,面积比电容可达到10.15 F/cm~2,且当电流密度增大到100 m A/cm~2时,面积电容仍然为7.29 F/cm~2,显示出优异的电容保持率;当NiCo_2S_4负载量是14.8 mg时,电流密度为20 m A/cm~2,充放电5 000次,电容保持率是72.5%,显示出NiCo_2S_4@泡沫镍电极良好的循环稳定性。     

Ionic Liquid‐Directed Nanoporous TiNb2O7 Anodes with Superior Performance for Fast‐Rechargeable Lithium‐Ion Batteries

Nanoporous TiNb₂O₇ (NPTNO) material is synthesized by a sol–gel method with an ionic liquid (IL) as the nanoporous structure directing template. NPTNO exhibits a high reversible capacity of 210 mAh g^–1 even at the charging rate of 50 C and an excellent cyclability of half‐cell capacity retention of 74% for 1000 cycles at 5 C and LiNi_0.5Mn_1.5O₄‐coupled full‐cell capacity retentions of 81% and 87% for 1000 cycles at 1 C and 2 C, respectively. The studies of the 1000 cycled NPTNO electrode illustrate that the IL‐directed mesoporous structure can enhance the cyclability of NPTNO cells due to the alleviation of repetitive mechanical stress and volume fluctuation induced by the repetitive Li⁺ insertion‐extraction processes. The measured Li⁺ diffusion coefficients from the galvanostatic intermittent titration technique suggest that the IL‐templating strategy indeed ensures the fast rechargeability of NPTNO cells based on the fast Li⁺ diffusion kinetics. Benefitting from the nanoporous structure, NPTNO with unhindered Li⁺ diffusion pathways achieves a superior rate capability in the titanium‐based oxide materials and the best full‐cell cyclability in the TNO materials. Therefore, the templating potential of IL is demonstrated, and the superb electrochemical performance establishes the IL‐directed NPTNO as a promising anode candidate for fast‐rechargeable LIBs.     

One‐Step Hydrothermal Tailoring of NiCo2S4 Nanostructures on Conducting Oxide Substrates as an Efficient Counter Electrode in Dye‐Sensitized Solar Cells

A one‐step in situ tailoring of NiCo₂S₄ nanostructures is demonstrated on fluorine‐doped tin oxide (FTO) as Pt‐free counter electrodes (CEs) for dye‐sensitized solar cells (DSSCs) with performance surpassing that of a conventional Pt‐sputtered CE. An interconnected NiCo₂S₄ nanosheet network is successfully constructed on the FTO glass via a hydrothermal method, attributed to the synergistic effect of structure‐directing hexamethylenetetramine and L‐cysteine. A growth mechanism is proposed, and the effects of nanostructures and sulfur atomic percentages on the electrocatalytic performance are discussed in depth. A DSSC with the optimized interconnected NiCo₂S₄ nanosheet CE exhibits higher power conversion efficiency (7.22%) compared to that with a conventional Pt‐sputtered CE (6.87%) due to excellent charge transport properties and enhanced electrocatalytic activity of the NiCo₂S₄ nanostructures. This work showcases the strong potential of nanostructured ternary chalcogenides, which are composed of earth‐abundant elements and prepared through a single‐step hydrothermal process without tedious posttreatments, to reduce the dependence of platinum in DSSCs and other electrochemical devices.