A Microwave Synthesis of Mesoporous NiCo2O4 Nanosheets as Electrode Materials for Lithium‐Ion Batteries and Supercapacitors

A facile microwave method was employed to synthesize NiCo₂O₄ nanosheets as electrode materials for lithium‐ion batteries and supercapacitors. The structure and morphology of the materials were characterized by X‐ray diffraction, field‐emission scanning electron microscopy, transmission electron microscopy and Brunauer–Emmett–Teller methods. Owing to the porous nanosheet structure, the NiCo₂O₄ electrodes exhibited a high reversible capacity of 891 mA h g^?1 at a current density of 100 mA g^?1, good rate capability and stable cycling performance. When used as electrode materials for supercapacitors, NiCo₂O₄ nanosheets demonstrated a specific capacitance of 400 F g^?1 at a current density of 20 A g^?1 and superior cycling stability over 5000 cycles. The excellent electrochemical performance could be ascribed to the thin porous structure of the nanosheets, which provides a high specific surface area to increase the electrode–electrolyte contact area and facilitate rapid ion transport.     

Hierarchical NiCo2S4 Nanotube@NiCo2S4 Nanosheet Arrays on Ni Foam for High‐Performance Supercapacitors

Hierarchical NiCo₂S₄ nanotube@NiCo₂S₄ nanosheet arrays on Ni foam have been successfully synthesized. Owing to the unique hierarchical structure, enhanced capacitive performance can be attained. A specific capacitance up to 4.38 F cm^?2 is attained at 5 mA cm^?2, which is much higher than the specific capacitance values of NiCo₂O₄ nanosheet arrays, NiCo₂S₄ nanosheet arrays and NiCo₂S₄ nanotube arrays on Ni foam. The hierarchical NiCo₂S₄ nanostructure shows superior cycling stability; after 5000 cycles, the specific capacitance still maintains 3.5 F cm^?2. In addition, through the morphology and crystal structure measurement after cycling stability test, it is found that the NiCo₂S₄ electroactive materials are gradually corroded; however, the NiCo₂S₄ phase can still be well‐maintained. Our results show that hierarchical NiCo₂S₄ nanostructures are suitable electroactive materials for high performance supercapacitors.     

Enhanced specific energy of silver-doped MnO2/graphene oxide electrodes as facile fabrication symmetric supercapacitor device

The present work is about the preparation of silver (Ag)-doped manganese oxide (MnO₂)/graphene oxide (GO) composite thin films are deposited by a facile and binder-free successive ionic layer adsorption and reaction (SILAR) method for the first time. The Brunauer-Emmett-Teller (BET) study revealed the nanosheets of MnO₂–Ag3/GO exhibit high specific surface area of 192 m² g^?1. The tailored flower-like morphology and interconnected nanosheets of MnO₂–Ag3/GO electrodes achieved high electrochemical performance. The maximum specific capacitance (Cs) of 877 F g^?1 at the scan rate of 5 mV s^?1 is obtained for MnO₂–Ag3/GO electrode tested in 1 M sodium sulfate (Na₂SO₄) electrolyte with capacity retention of 94.57% after 5000 cycling stability. The MnO₂–Ag3/GO composite-based flexible solid state symmetric supercapacitor (FSS-SSC) device delivered Cs as 164 F g^?1 with specific energy of 57 Wh kg^?1 at specific power of 1.6 kW kg^?1 and capacitive retention of 94% after 10,000 cycles.     

MnO_2/NiCo_2O_4的静电自组装合成及其电化学性能

通过带负电荷的MnO2纳米片与带正电荷的Co-Ni层状双氢氧化物(LDHs)纳米片的静电自组装外加后续热处理合成了异质层状结构的MnO2/NiCo2O4复合物.采用X射线衍射(XRD)、傅里叶变换红外(FTIR)光谱、拉曼光谱、原子吸收光谱(AAS)、场发射扫描电镜(FESEM)和透射电子显微镜(TEM)对其结构和形貌进行了表征.用循环伏安(CV)、恒流充放电和电化学交流阻抗技术对其电化学性能进行了测试.研究结果表明,该方法制得的异质复合物具有多孔层状堆垛结构,这种特殊的结构不仅增大了电解液离子的接触面积,而且还为其嵌入-脱出提供了有效途径.该复合物在1 A·g-1电流密度时,-0.6-0.45 V电位窗口内的比电容达482 F·g-1,优于纯组分MnO2和NiCo2O4的电容性能.     

GO/ZIF-67模板制备rGO/NiCo2S4及高性能不对称超级电容器

以氧化石墨烯(GO)为基底,在GO表面原位生长ZIF-67并作为模板,经硝酸镍刻蚀、碳化、水热硫化制得rGO/NiCo_2S_4复合材料。采用X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)表征复合材料的结构与形貌。随后将rGO/NiCo_2S_4复合材料制成正极材料,测试其电化学性能,测试结果显示:rGO/NiCo_2S_4-1.5 h电极材料在1 A·g~(-1)的电流密度下,其比电容值高达1 577 F·g~(-1),当电流密度达到10 A·g~(-1)时,倍率性能为86.4%,在10 A·g~(-1)的电流密度下循环2 000次后,电容保持率为76.9%。另外,在6 mol·L-1KOH电解液中,由AC//rGO/NiCo_2S_4-1.5 h组成的不对称电容器在功率密度为723 W·kg~(-1)时,能量密度为33 Wh·kg~(-1);在高功率密度为7 277 W·kg~(-1)时,能量密度仍保持为23 Wh·kg~(-1)。     

NiCo2O4 nanosheets supported on Ni foam for rechargeable nonaqueous sodium–air batteries

NiCo₂O₄ nanosheets supported on Ni foam were synthesized by a solvothermal method. A composite of NiCo₂O₄ nanosheets/Ni as a carbon-free and binder-free air cathode exhibited an initial discharge capacity of 1762 mAh g^− 1 with a low polarization of 0.96 V at 20 mA g^− 1 for sodium–air batteries. Na₂O₂ nanosheets were firstly observed as the discharged product in sodium–air battery. High electrocatalytic activity of NiCo₂O₄ nanosheets/Ni made it a promising air electrode for rechargeable sodium–air batteries.     

Solvothermal synthesis of hierarchical SnIn4S8 microspheres and their application in photocatalysis

Hierarchical SnIn₄S₈ microspheres were successfully fabricated via a solvothermal method without the assistance of any templates or surfactants. These microspheres were of a new tetragonal polymorph, distinct from the cubic counterpart popularly reported in the literature. Systematic characterization indicated that these microspheres exhibited a diameter of 2?C4 ??m and were assembled by numerous interconnected nanosheets of 40 nm thickness. The formation mechanism of hierarchical SnIn₄S₈ microspheres was proposed by taking into account the influences of experimental conditions on the morphology and structure. Hierarchical microspheres possessed a large specific surface area of 197 m² g^?1 and an accessible porous configuration, which gave rise to an excellent visible light-driven photocatalytic efficiency for methyl orange degradation in aqueous solutions, superior to that for the known N-doped TiO₂ photocatalyst.     

ZIFs骨架型双壳层纳米笼状CoS/NiCo2S4的制备及其电化学性能

采用离子刻蚀和化学气相沉积法制备出具有沸石咪唑酯骨架(ZIFs)型双壳层纳米笼状的CoS/NiCo_2S_4并组装成超级电容器。该结构有较大的比表面积(98 m2·g-1),合适的孔道(孔径4 nm),且保留了ZIFs骨架构型。作为电极活性材料时,具有良好的结构稳定性和电化学活性,有利于增强所组装的超级电容器的循环稳定性和比容量。在三电极体系中,在1 A·g-1的电流密度下,容量为1 230 F·g-1;在3 A·g-1电流密度下循环9 000圈后,初始电容保持率为76.6%。在以该电极、活性炭电极与KOH/聚乙烯醇(PVA)凝胶态电解质组装的器件中,当功率密度为702 W·kg-1时,能量密度达31.6 Wh·kg-1;在7 056 W·kg-1的高功率密度下,仍保持16.5 Wh·kg-1的能量密度。     

纳米多孔双金属氧化物NiCo2O4的制备及其电化学性能

采用快速凝固与脱合金化相结合的方法制备纳米多孔Ni、Ni-Co合金,分别经腐蚀与退火获得纳米多孔NiO、NiCo_2O_4,采用XRD、SEM、TEM、N_2吸附-脱附等对多孔NiO、NiCo_2O_4电极的物相、形貌结构、孔径分布进行表征,并通过循环伏安、恒电流充放电等方法测试多孔电极的电化学性能。结果表明,得到的纳米多孔NiO具有均匀的"泥裂"式结构,在1A·g~(-1)电流密度下比电容为375 F·g~(-1),当电流密度增加至20 A·g~(-1)时的比容保持率为67.5%,在4 A·g~(-1)电流密度下循环充放电1 000次,比容保持率为81.7%;NiCo_2O_4形成典型的开放式纳米多孔双连续结构,其在1A·g~(-1)电流密度下比电容为674 F·g~(-1),当电流密度增加至20 A·g~(-1),比容保持率达72.0%;在4 A·g~(-1)电流密度下循环充放电1 000次,比容保持率达92.9%,双连续纳米多孔结构及其提供的机械稳定性,使得NiCo_2O_4表现出更为优异的超电容性能。     

Hierarchical ZnCo2O4@NiCo2O4 Core–Sheath Nanowires: Bifunctionality towards High‐Performance Supercapacitors and the Oxygen‐Reduction Reaction

Increasing energy demands and worsening environmental issues have stimulated intense research on alternative energy storage and conversion systems including supercapacitors and fuel cells. Here, a rationally designed hierarchical structure of ZnCo₂O₄@NiCo₂O₄ core–sheath nanowires synthesized through facile electrospinning combined with a simple co‐precipitation method is proposed. The obtained core–sheath nanostructures consisting of mesoporous ZnCo₂O₄ nanowires as the core and uniformly distributed ultrathin NiCo₂O₄ nanosheets as the sheath, exhibit excellent electrochemical activity as bifunctional materials for supercapacitor electrodes and oxygen reduction reaction (ORR) catalysts. Compared with the single component of either ZnCo₂O₄ nanowires or NiCo₂O₄ nanosheets, the hierarchical ZnCo₂O₄@NiCo₂O₄ core–sheath nanowires demonstrate higher specific capacitance of 1476 F g^?1 (1 A g^?1) and better rate capability of 942 F g^?1 (20 A g^?1), while maintaining 98.9 % capacity after 2000 cycles at 10 A g^?1. Meanwhile, the ZnCo₂O₄@NiCo₂O₄ core–sheath nanowires reveal comparable catalytic activity but superior stability and methanol tolerance over Pt/C as ORR catalyst. The impressive performance may originate from the unique hierarchical core–sheath structures that greatly facilitate enhanced reactivity, and faster ion and electron transfer.     

NiO/MnO_2分级纳米片阵列复合材料的制备与超电容性能

通过化学浴沉积和水热法在泡沫镍上制备了NiO/MnO_2分级纳米片阵列复合材料,XRD和SEM测试表明NiO纳米片垂直生长在泡沫镍上,交叉形成网状阵列结构;MnO_2纳米介孔泡沫进一步生长在NiO纳米片两侧,与NiO形成了壳核式的复合结构。循环伏安和恒流充放电测试发现,NiO/MnO_2分级纳米片阵列复合材料的电化学性能相比复合前得到明显改善,在1 A·g~(-1)的电流密度下,比电容提高至1 297 F·g~(-1);2 A·g~(-1)下循环1 000次,比电容保持率高达97%,比电容和循环性能的改善是由于分级纳米片阵列复合结构方便了电解液传质,扩大了活性材料与电解液的接触,促进了赝电容反应,提高了NiO和MnO_2的结构稳定性。     

NiO/MnO2分级纳米片阵列复合材料的制备与超电容性能

通过化学浴沉积和水热法在泡沫镍上制备了NiO/MnO₂分级纳米片阵列复合材料,XRD和SEM测试表明NiO纳米片垂直生长在泡沫镍上,交叉形成网状阵列结构;MnO₂纳米介孔泡沫进一步生长在NiO纳米片两侧,与NiO形成了壳核式的复合结构。循环伏安和恒流充放电测试发现,NiO/MnO₂分级纳米片阵列复合材料的电化学性能相比复合前得到明显改善,在1 A·g^-1的电流密度下,比电容提高至1 297 F·g^-1;2 A·g^-1下循环1 000次,比电容保持率高达97%,比电容和循环性能的改善是由于分级纳米片阵列复合结构方便了电解液传质,扩大了活性材料与电解液的接触,促进了赝电容反应,提高了NiO和MnO₂的结构稳定性。     

Two‐Dimensional Cobalt‐/Nickel‐Based Oxide Nanosheets for High‐Performance Sodium and Lithium Storage

Two‐dimensional (2D) nanomaterials are one of the most promising types of candidates for energy‐storage applications due to confined thicknesses and high surface areas, which would play an essential role in enhanced reaction kinetics. Herein, a universal process that can be extended for scale up is developed to synthesise ultrathin cobalt‐/nickel‐based hydroxides and oxides. The sodium and lithium storage capabilities of Co₃O₄ nanosheets are evaluated in detail. For sodium storage, the Co₃O₄ nanosheets exhibit excellent rate capability (e.g., 179 mA h g^?1 at 7.0 A g^?1 and 150 mA h g^?1 at 10.0 A g^?1) and promising cycling performance (404 mA h g^?1 after 100 cycles at 0.1 A g^?1). Meanwhile, very impressive lithium storage performance is also achieved, which is maintained at 1029 mA h g^?1 after 100 cycles at 0.2 A g^?1. NiO and NiCo₂O₄ nanosheets are also successfully prepared through the same synthetic approach, and both deliver very encouraging lithium storage performances. In addition to rechargeable batteries, 2D cobalt‐/nickel‐based hydroxides and oxides are also anticipated to have great potential applications in supercapacitors, electrocatalysis and other energy‐storage‐/‐conversion‐related fields.     

Morphology‐Tuned Synthesis of NiCo2O4‐Coated 3D Graphene Architectures Used as Binder‐Free Electrodes for Lithium‐Ion Batteries

Nanostructured NiCo₂O₄ is directly grown on the surface of three‐dimensional graphene‐coated nickel foam (3D‐GNF) by a facile electrodeposition technique and subsequent annealing. The resulting NiCo₂O₄ possesses a distinct flower or sheet morphology, tuned by potential or current variation electrodeposition, which are used as binder‐free lithium‐ion battery anodes for the first time. Both samples exhibit high lithium storage capacity, profiting from the unique binder‐free electrode structures. The flower‐type NiCo₂O₄ demonstrates high reversible discharge capacity (1459 mAh g^?1 at 200 mA g^?1) and excellent cyclability with around 71 % retention of the reversible capacity after 60 cycles, which are superior to the sheet‐type NiCo₂O₄. Such superb performance can be attributed to high volume utilization efficiency with unique morphological character, a well‐preserved connection between the active materials and the current collector, a short lithium‐ion diffusion path, and fast electrolyte transfer in the binder‐free NiCo₂O₄‐coated 3D graphene structure. The simple preparation process and easily controllable morphology make the binder‐free NiCo₂O₄/3D‐GNF hybrid a potential material for commercial applications.     

Synthesis of porous biocarbon supported Ni3S4/CeO2 nanocomposite as high-efficient electrode materials for asymmetric supercapacitors

Biocarbon-supported polymetallic composites (CAS@Ni₃S₄/CeO₂) were fabricated by a facile hydrothermal process. The as-prepared CAS@Ni₃S₄/CeO₂ materials integrated the advantages of transition metal sulfides (good conductivity), rare-earth metal oxides (excellent stability), as well as porous carbon with high surface area, thus exhibiting promising electrochemical performance in supercapacitor applications. Indeed, the optimal CAS@Ni₃S₄/CeO₂-150 composite displayed a high specific capacitance of 1364 F g^?1 and impressive cycle performance with capacitance retention of 93.81 % after 10,000 cycles. The calculation of capacitance contribution showed that the satisfying behavior of the electrode was a combination of the diffusion process and the surface capacitance characteristics. Furthermore, the assembled asymmetric supercapacitor (CAS@Ni₃S₄/CeO₂-150//CAS) delivered an ultrahigh energy density of 102.76 Wh kg^?1, which was better than that of the commercial activated carbon-based ASC device. This novel strategy might provide a new perspective for transition metal sulfide/rare earth metal oxide composite in the electrochemical energy storage field.     

All-solid-state flexible asymmetric supercapacitors with high energy and power densities based on NiCo_2S_4@MnS and active carbon

Electrode material based on a novel core–shell structure consisting of NiCo_2S_4(NCS) solid fiber core and Mn S(MS) sheet shell(NCS@MS) in situ grown on carbon cloth(CC) has been successfully prepared by a simple sulfurization-assisted hydrothermal method for high performance supercapacitor. The synthesized NiCo_2S_4@Mn S/CC electrode shows high capacitance of 1908.3 F g~(-1) at a current density of 0.5 A g~(-1) which is higher than those of NiCo_2S_4 and Mn S at the same current density. A flexible all-solid-state asymmetric supercapacitor(ASC) is constructed by using NiCo_2S_4@Mn S/CC as positive electrode, active carbon/CC as negative electrode and KOH/poly(vinyl alcohol)(PVA) as electrolyte. The optimized ASC shows a maximum energy density of 23.3 Wh kg~(-1) at 1 A g~(-1), a maximum power density of about7.5 kw kg~(-1) at 10 A g~(-1) and remarkable cycling stability. After 9000 cycles, the ASC still exhibited67.8% retention rate and largely unchanged charge/discharge curves. The excellent electrochemical properties are resulted from the novel core–shell structure of the NiCo_2S_4@Mn S/CC electrode, which possesses both high surface area for Faraday redox reaction and superior kinetics of charge transport. The NiCo_2S_4@Mn S/CC electrode shows a promising potential for energy storage applications in the future.     

Surface domain potential difference-mediated efficient charge separation on a defective ZnIn2S4 microsphere photocatalyst

Low-efficiency charge separation in metal sulfides is a major obstacle to realizing high photocatalytic performance. Herein, we propose the concept of a similar surface domain potential difference between adjacent microdomains with and without surface S vacancies on ZnIn₂S₄ to mediate charge separation. Defective ZnIn₂S₄ microspheres (DZISNPs) are prepared through a solvothermal method combined with a low-temperature hydrogenation surface engineering strategy. The as-prepared DZISNPs with a narrowed bandgap of 2.38 eV possess a large specific surface area of 178.5 m² g^?1, a pore size of 6.89 nm, and a pore volume of 0.36 cm³ g^?1, which further improves the visible light absorption. The resultant DZISNPs exhibit excellent visible light activity (2.15 mmol h^?1 g^?1), which is ～two-fold higher than that of the original DZISNP. The experimental results and DFT calculations reveal that the enhanced property can be a result of the surface S vacancy-induced surface domain potential difference, promoting the spatial separation of electrons and holes. Furthermore, the long-term stability of the DZISNPs indicates that the formation of surface S vacancies can inhibit the photocorrosion of ZnIn₂S₄. This strategy provides new insights for fabricating highly efficient and stable sulfide photocatalysts.     

Reduced Graphene Oxide‐Supported TiO2 Fiber Bundles with Mesostructures as Anode Materials for Lithium‐Ion Batteries

Although the synthesis of mesoporous materials is well established, the preparation of TiO₂ fiber bundles with mesostructures, highly crystalline walls, and good thermal stability on the RGO nanosheets remains a challenge. Herein, a low‐cost and environmentally friendly hydrothermal route for the synthesis of RGO nanosheet‐supported anatase TiO₂ fiber bundles with dense mesostructures is used. These mesostructured TiO₂‐RGO materials are used for investigation of Li‐ion insertion properties, which show a reversible capacity of 235 mA h g^?1 at 200 mA g^?1 and 150 mA h g^?1 at 1000 mA g^?1 after 1000 cycles. The higher specific surface area of the new mesostructures and high conductive substrate (RGO nanosheets) result in excellent lithium storage performance, high‐rate performance, and strong cycling stability of the TiO₂‐RGO composites.     

Hierarchical Porous NiCo2O4 Microboxes Constructed by Low-Dimensional Substructures for Electrochemical Supercapacitor

The design and synthesis of new materials/structures for high-performance electrochemical capacitors (ECs) is an ongoing challenge. Herein, a hierarchical porous NiCo₂O₄ microbox superstructure made of low-dimensional substructures was reported. The as-prepared NiCo₂O₄ microboxes are constructed by 2D nanosheets building units, which are futher woven by 0D nanoparticles and 1D nanowires. Such microbox superstructures combine the merits of all material dimensions in electrochemical capacitors, such as high porosity, sufficient active sites, and fast mass and charge transport. Benefiting from the structural advantages, the resultant NiCo₂O₄ microbox electrode exhibits ultra-high capacitor performance, i.e., the initial capacitance of 1820 F · g^–1 and 96.6 % capacitance retention after 4000 cycles at 5 A · g^–1.     

Toward high-performance Li storage anodes: design and construction of spherical carbon-coated CoNiO2 materials

CoNiO₂ nanosheets were prepared by a simple hydrothermal process, and then the spherical CoNiO₂@C micro-nano structures composed of nanoparticles were designed by morphology reshaping for the first time. The results show that the carbon coating changes the morphology of CoNiO₂, and the CoNiO₂@C composite shows porous microsphere structure consisted of nanoparticles. The porous structure combined with highly conductive carbon shell indicates an improved electronic conductivity and charge transfer. The carbon shell decreases the charge-transfer resistance of CoNiO₂, and thus enhances the kinetic performances. The pristine CoNiO₂ and CoNiO₂@C (3, 5, and 10 wt%) composites deliver charge/discharge capacities of 511.7/526.9, 811.3/826.3, 997.1/1013.1, and 1216.1/1241.8 mAh g^?1 at 500 mA g^?1 after 200 cycles, respectively. The carbon coating improves the reversible capacity, rate capability, and cycle performance of CoNiO₂, especially at high rates. The improved rate performance, excellent cycle performance, and high kinetic performances are ascribed to the elaborate design of architecture and composition. Hence, such porous CoNiO₂@C microsphere consisted of nanoparticles can be regarded as promising candidates as anode materials for lithium-ion battery.