Ultrathin ZnS nanosheet/carbon nanotube hybrid electrode for high-performance flexible all-solid-state supercapacitor

Flexible and easily reconfigurable supercapacitors show great promise for application in wearable electronics.In this study,multiwall C nanotubes (CNTs) decorated with hierarchical ultrathin zinc sulfide (ZnS) nanosheets (ZnS@CNT) are synthesized via a facile method.The resulting ZnS@CNT electrode,which delivers a high specific capacitance of 347.3 F·g-1 and an excellent cycling stability,can function as a high-performance electrode for a flexible all-solid-state supercapacitor using a polymer gel electrolyte.Our device exhibits a remarkable specific capacitance of 159.6 F·g-1,a high energy density of 22.3 W·h·kg-1 and a power density of 5 kW·kg-1.It also has high electrochemical performance even under bending or twisting.The all-solid-state supercapacitors can be easily integrated in series to power different commercial light-emitting diodes without an external bias voltage.     

高比容纳米Ni（OH）2的制备及其电化学电容性能

以草酸和乙酸镍为原料,通过低温固相法合成前驱体(NiC2O4.2H2O)粉末。用此前驱体粉末与固态NaOH混合并充分研磨制得纳米Ni(OH)2粉末。经SEM、XRD测试表明,制得的纳米Ni(OH)2粉末是平均粒径约为12nm的β-Ni(OH)2。用循环伏安法、恒流充放电测试和交流阻抗谱研究Ni(OH)2电极的电化学电容特性。结果表明在电流密度为1A.g-1时,其比电容高达2271F.g-1,且经多次循环后表现出较好的循环稳定性能。     

Highly Concentrated,Ultrathin Nickel Hydroxide Nanosheet Ink for Wearable Energy Storage Devices

Solution‐based techniques are considered as a promising strategy for scalable fabrication of flexible electronics owing to their low‐cost and high processing speed. The key to the success of these techniques is dominated by the ink formulation of active nanomaterials. This work successfully prepares a highly concentrated two dimensional (2D) crystal ink comprised of ultrathin nickel hydroxide (Ni(OH)₂) nanosheets with an average lateral size of 34 nm. The maximum concentration of Ni(OH)₂ nanosheets in water without adding any additives reaches as high as 50 mg mL^?1, which can be printed on arbitrary substrates to form Ni(OH)₂ thin films. As a proof‐of‐concept application, Ni(OH)₂ nanosheet ink is coated on commercialized carbon fiber yarns to fabricate wearable energy storage devices. The thus‐fabricated hybrid supercapacitors exhibit excellent flexibility with a capacitance retention of 96% after 5000 bending–unbending cycles, and good weavability with a high volumetric capacitance of 36.3 F cm^?3 at a current density of 0.4 A cm^?3, and an energy density of 11.3 mWh cm^?3 at a power density of 0.3 W cm^?3. As a demonstration of practical application, a red light emitting diode can be lighted up by three hybrid devices connected in series.     

Extremely high-rate aqueous supercapacitor fabricated using doped carbon nanoflakes with large surface area and mesopores at near-commercial mass loading

Achieving a satisfactory energy-power combination in a supercapacitor that is based on all-carbon electrodes and operates in benign aqueous media instead of conventional organic electrolytes is a major challenge.For this purpose,we fabricated carbon nanoflakes (20-100 nm in thickness,5-μm in width) containing an unparalleled combination of a large surface area (3,000 m2·g-1 range) and mesoporosity (up to 72％).These huge-surface area functionalized carbons (HSAFCs) also had a substantial oxygen and nitrogen content (～10 wt.％ combined),with a significant fraction of redox-active carboxyl/phenol groups in an optimized specimen.Their unique structure and chemistry resulted from a tailored single-step carbonization-activation approach employing (2-benzimidazolyl) acetonitrile combined with potassium hydroxide (KOH).The HSAFCs exhibited specific capacitances of 474 F·g-1 at 0.5 A·g-1 and 285 F·g-1 at 100 A·g-1 (charging time ＜ 3 s) in an aqueous 2 M KOH solution.These values are among the highest reported,especially at high currents.When tested with a stable 1.8-V window in a 1 M Na2SO4 electrolyte,a symmetric supercapacitor device using the fabricated nanoflakes as electrodes yielded a normalized active mass of 24.4 Wh·kg-1 at 223 W·kg-1 and 7.3 Wh·kg-1 at 9,360 W·kg-1.The latter value corresponds to a charge time of ＜3 s.The cyclability of the devices was excellent,with 93％ capacitance retention after 10,000 cycles.All the electrochemical results were achieved by employing electrodes with near-commercial mass loadings of 8 mg·cm-2.     

High‐Stacking‐Density,Superior‐Roughness LDH Bridged with Vertically Aligned Graphene for High‐Performance Asymmetric Supercapacitors

The high‐performance electrode materials with tuned surface and interface structure and functionalities are highly demanded for advanced supercapacitors. A novel strategy is presented to conFigure high‐stacking‐density, superior‐roughness nickel manganese layered double hydroxide (LDH) bridged by vertically aligned graphene (VG) with nickel foam (NF) as the conductive collector, yielding the LDH‐NF@VG hybrids for asymmetric supercapacitors. The VG nanosheets provide numerous electron transfer channels for quick redox reactions, and well‐developed open structure for fast mass transport. Moreover, the high‐stacking‐density LDH grown and assembled on VG nanosheets result in a superior hydrophilicity derived from the tuned nano/microstructures, especially microroughness. Such a high stacking density with abundant active sites and superior wettability can be easily accessed by aqueous electrolytes. Benefitting from the above features, the LDH‐NF@VG can deliver a high capacitance of 2920 F g^?1 at a current density of 2 A g^?1, and the asymmetric supercapacitor with the LDH‐NF@VG as positive electrode and activated carbon as negative electrode can deliver a high energy density of 56.8 Wh kg^?1 at a power density of 260 W kg^?1, with a high specific capacitance retention rate of 87% even after 10 000 cycles.     

NiS2/三维多孔石墨烯复合材料作为超级电容器电极材料的电化学性能

选用合适的软模板,通过简便的一步溶剂热法成功制备了NiS₂/三维多孔石墨烯（3D rGO）复合材料。利用FESEM、TEM、XPS和电化学工作站对样品的表面形貌、元素价态和电化学性能进行表征。结果表明:制备的NiS₂/3D rGO复合材料存在石墨烯三维堆叠的孔道结构,且具备较大的比表面积,为57.51 m2g-1。电化学测试表明,在1 Ag-1的电流密度下NiS₂/3D rGO复合材料的比电容高达1 116.7 Fg-1,而且当电流密度增加到5 Ag-1时NiS₂/3D rGO复合材料的比电容为832.2 Fg-1,比电容保持率为1 Ag-1时的74.5%。在4 Ag-1电流密度下,经过1 000次循环后,NiS₂/3D rGO复合材料的比电容仍能保持91.2%。因此,NiS₂/3D rGO复合材料可作为一种理想的超级电容器电极材料。      

Ultrathin 2D Metal–Organic Framework Nanosheets In situ Interpenetrated by Functional CNTs for Hybrid Energy Storage Device

The controllable construction of two-dimensional(2D)metal–organic framework(MOF)nanosheets with favorable electrochemical performances is greatly challenging for energy storage.Here,we design an in situ induced growth strategy to construct the ultrathin carboxylated carbon nanotubes(C-CNTs)interpenetrated nickel MOF(Ni-MOF/C-CNTs)nanosheets.The deliberate thickness and specific surface area of novel 2D hybrid nanosheets can be effectively tuned via finely controlling C-CNTs involvement.Due to the unique microstructure,the integrated 2D hybrid nanosheets are endowed with plentiful electroactive sites to promote the electrochemical performances greatly.The prepared Ni-MOF/C-CNTs nanosheets exhibit superior specific capacity of 680 C g^−1 at 1 A g^−1 and good capacity retention.The assembled hybrid device demonstrated the maximum energy density of 44.4 Wh kg^−1 at a power density of 440 W kg^−1.Our novel strategy to construct ultrathin 2D MOF with unique properties can be extended to synthesize various MOF-based functional materials for diverse applications.     

Biomass‐Derived Nitrogen‐Doped Carbon Nanofiber Network: A Facile Template for Decoration of Ultrathin Nickel‐Cobalt Layered Double Hydroxide Nanosheets as High‐Performance Asymmetric Supercapacitor Electrode

The development of biomass‐based energy storage devices is an emerging trend to reduce the ever‐increasing consumption of non‐renewable resources. Here, nitrogen‐doped carbonized bacterial cellulose (CBC‐N) nanofibers are obtained by one‐step carbonization of polyaniline coated bacterial cellulose (BC) nanofibers, which not only display excellent capacitive performance as the supercapacitor electrode, but also act as 3D bio‐template for further deposition of ultrathin nickel‐cobalt layered double hydroxide (Ni‐Co LDH) nanosheets. The as‐obtained CBC‐N@LDH composite electrodes exhibit significantly enhanced specific capacitance (1949.5 F g^?1 at a discharge current density of 1 A g^?1, based on active materials), high capacitance retention of 54.7% even at a high discharge current density of 10 A g^?1 and excellent cycling stability of 74.4% retention after 5000 cycles. Furthermore, asymmetric supercapacitors (ASCs) are constructed using CBC‐N@LDH composites as positive electrode materials and CBC‐N nanofibers as negative electrode materials. By virtue of the intrinsic pseudocapacitive characteristics of CBC‐N@LDH composites and 3D nitrogen‐doped carbon nanofiber networks, the developed ASC exhibits high energy density of 36.3 Wh kg^?1 at the power density of 800.2 W kg^?1. Therefore, this work presents a novel protocol for the large‐scale production of biomass‐derived high‐performance electrode materials in practical supercapacitor applications.     

MOF‐Derived Hollow Cage NixCo3−xO4 and Their Synergy with Graphene for Outstanding Supercapacitors

Highly optimized nickel cobalt mixed oxide has been derived from zeolite imidazole frameworks. While the pure cobalt oxide gives only 178.7 F g^?1 as the specific capacitance at a current density of 1 A g^?1, the optimized Ni:Co 1:1 has given an extremely high and unprecedented specific capacitance of 1931 F g^?1 at a current density of 1 A g^?1, with a capacitance retention of 69.5% after 5000 cycles in a three electrode test. This optimized Ni:Co 1:1 mixed oxide is further used to make a composite of nickel cobalt mixed oxide/graphene 3D hydrogel for enhancing the electrochemical performance by virtue of a continuous and porous graphene conductive network. The electrode made from GNi:Co 1:1 successfully achieves an even higher specific capacitance of 2870.8 F g^?1 at 1 A g^?1 and also shows a significant improvement in the cyclic stability with 81% capacitance retention after 5000 cycles. An asymmetric supercapacitor is also assembled using a pure graphene 3D hydrogel as the negative electrode and the GNi:Co 1:1 as the positive electrode. With a potential window of 1.5 V and binder free electrodes, the capacitor gives a high specific energy density of 50.2 Wh kg^?1 at a high power density of 750 W kg^?1.     

Freestanding hierarchical porous carbon film derived from hybrid nanocellulose for high-power supercapacitors

Nanocellulose is a sustainable and eco-friendly nanomaterial derived from renewable biomass.In this study,we utilized the structural advantages of two types of nanocellulose and fabricated freestanding carbonized hybrid nanocellulose films as electrode materials for supercapacitors.The long cellulose nanofibrils (CNFs) formed a macroporous framework,and the short cellulose nanocrystals were assembled around the CNF framework and generated micro/mesopores.This two-level hierarchical porous structure was successfully preserved during carbonization because of a thin atomic layer deposited (ALD) Al2O3 conformal coating,which effectively prevented the aggregation of nanocellulose.These carbonized,partially graphitized nanocellulose fibers were interconnected,forming an integrated and highly conductive network with a large specific surface area of 1,244 m2·g-1.The two-level hierarchical porous structure facilitated fast ion transport in the film.When tested as an electrode material with a high mass loading of 4 mg·cm-2 for supercapacitors,the hierarchical porous carbon film derived from hybrid nanocellulose exhibited a specific capacitance of 170 F.g-1and extraordinary performance at high current densities.Even at a very high current of 50 A·g-1,it retained 65％ of its original specific capacitance,which makes it a promising electrode material for high-power applications.     

Self‐Assembled Nickel Pyrophosphate‐Decorated Amorphous Bimetal Hydroxides 2D‐on‐2D Nanostructure for High‐Energy Solid‐State Asymmetric Supercapacitor

To obtain a supercapacitor with a remarkable specific capacitance and rate performance, a cogent design and synthesis of the electrode material containing abundant active sites is necessary. In present work, a scalable strategy is developed for preparing 2D‐on‐2D nanostructures for high‐energy solid‐state asymmetric supercapacitors (ASCs). The self‐assembled vertically aligned microsheet‐structured 2D nickel pyrophosphate (Ni₂P₂O₇) is decorated with amorphous bimetallic nickel cobalt hydroxide (NiCo‐OH) to form a 2D‐on‐2D nanostructure arrays electrode. The resulting Ni₂P₂O₇/NiCo‐OH 2D‐on‐2D array electrode exhibits peak specific capacity of 281 mA hg^?1 (4.3 F cm^?2), excellent rate capacity, and cycling stability over 10 000 charge–discharge cycles in the positive potential range. The excellent electrochemical features can be attributed to the high electrical conductivity and 2D layered structure of Ni₂P₂O₇ along with the Faradic capacitance of the amorphous NiCo‐OH nanosheets. The constructed Ni₂P₂O₇/NiCo‐OH//activated carbon based solid‐state ASC cell operates in a high voltage window of 1.8 V with an energy density of 78 Wh kg^?1 (1.065 mWh cm^?3) and extraordinary cyclic stability over 10 000 charge–discharge cycles with excellent energy efficiency (75%–80%) over all current densities. The excellent electrochemical performance of the prepared electrode and solid‐state ASC device offers a favorable and scalable pathway for developing advanced electrodes.     

A facile preparation of graphene/reduced graphene oxide/Ni(OH)2 two dimension nanocomposites for high performance supercapacitors

A Ni(OH)₂ composite with good electrochemical performances was prepared by a facile method. Ni(OH)₂ was homogeneously grown on the hydrophilic graphene/graphene oxide (G/GO) nanosheets, which can be prepared in large scale in my lab. Then G/GO/Ni(OH)₂ was reduced by L-Ascorbic acid to obtain G/RGO/Ni(OH)₂. Caused by the synergy effects among the components, the G/RGO/Ni(OH)₂ electrode showed good electrochemical properties. The G/RGO/Ni(OH)₂ electrode possessed a specific capacitance as high as 1510 F g⁻¹ at 2 A g⁻¹ and even 890 F g⁻¹ at 40 A g⁻¹. An asymmetric supercapacitor device consisting of G/RGO/Ni(OH)₂ and reduced graphene oxide (RGO) was installed and displayed a high energy density of 44.9 W h kg⁻¹ at the power energy density of 400.1 W kg⁻¹. It was verified that the G/GO nanosheets are ideal supporting material in supercapacitor.     

模板法中孔炭及其双电层电容性能(英文)

以乙酸镁和柠檬酸镁热解得到的MgO为模板,热塑性沥青为碳前驱体,采用程序升温一步炭化法(950℃,N2)制备了高比表面积中孔炭材料。尽管未进行活化,两种模板前驱体与沥青混合所制中孔炭材料均可获得非常高的比表面积。以这两种中孔炭作为双电层电容器的电极材料,在质量分数为30%的KOH电解液中测试其电化学性能。结果表明:这两种中孔炭电极均可得到较高的比电容量和理想的功率特性,尤其是柠檬酸镁作前驱体时,MgO与沥青质量比为4时得到的炭材料(MCP8/2)在20mA.g-1的电流密度下得到284F.g-1的比电容量,且在1000mA.g-1时仍能得到236F.g-1的比电容。交流阻抗测试表明:组装的双电层电容器的内部阻抗均小于3.5Ω。     

Metal-organic framework derived hierarchical NiCo2O4 triangle nanosheet arrays@SiC nanowires network/carbon cloth for flexible hybrid supercapacitors

To overcome the disadvantages of traditional powder electrodes,such as the insufficient performance,the aggregation of active materials,and the complex fabrication process,rationally constructing free-standing electrode materials with hierarchical architecture is an effective and promising method,which could further improve the electrochemical properties.Herein,using metal-organic framework nanoar-rays (MOFNAs) as self-sacrificial templates and SiC nanowires (SiCNWs) network as nanoscale conductive skeletons,we successfully fabricated the hierarchical core-shell SiCNws@NiCo2O4NAs on carbon cloth (CC)substrate.Taking advantages of structural merits,such as hierarchical porous triangle-like NiCo2O4NAs,the interwoven SiCNWs network and conductive CC substrate,when evaluated as a binder-free superca-pacitor electrode,the CC/SiCNWs@NiCo2O4NAs shows a high specific capacitance of 1604.7 F g-1 (specific capacity of 222.9 mA h g-1) at 0.5 A g 1,good rate performance,and excellent cycling stability.Signifi-cantly,the hybrid supercapacitor assembled with CC/SiCNWs@NiCo2O4NAs as the cathode and MOF derived CC/SiCNWs@CNAs as the anode,could deliver a high specific density of 49.9 W h kg-1 at a specific power of 800 W kg-1,stable cycling performance,and good flexibility.Impressively,this feasible strategy for fabricating hierarchical structure displays great potential in the field of energy storage.     

Biowaste derived porous carbon sponge for high performance supercapacitors

Here,an agricultural waste (the stem pith of helianthus annuus,SPHA) is firstly used as the precursor for preparing three-dimensional (3D) porous carbon sponge (PCS).The as-prepared 3D PCS (SPHA-700) pos-sesses unique sponge-like structure,large specific surface area (SSA) and high nitrogen doping level (4.52 at.％),which benefit the enhancement of conductivity (5.8 S cm-1) and wettability.As a binder-free elec-trode for solid-state symmetric supercapacitor,SPHA-700 delivers a relatively high specific capacitance of 137.1 F g-1 at 0.5 A g-1.Moreover,activated SPHA-700 (SPHA-ac-700-2) displays an even higher specific capacitance (403.6 F g-1 at 0.5 A g-1) in 6.0 M KOH electrolyte.The SPHA-ac-700-2-based symmetrical supercapacitor can offer high specific capacitance (271 F g-1 at 1 A g-1) and good rate capability (82.1％of capacitance retention at 1-80 A g-1) in 6.0 M KOH electrolyte,together with high energy density(23.3 Wh kg-1 at 450 W kg-1) in 1.0 M Na2SO4 electrolyte.Such excellent performance of SPHA-ac-700-2 is believed to have originated from the crushed sponge-like structure,O/N-co-doping (10.6 at.％ O and 3.3 at.％ N),high SSA,large total pore volume,and hierarchical pore structure.     

Wire-Shaped 3D-Hybrid Supercapacitors as Substitutes for Batteries

We report a wire-shaped three-dimensional(3D)-hybrid supercapacitor with high volumetric capacitance and high energy density due to an interconnected 3D-configuration of the electrode allowing for large number of electrochemical active sites,easy access of electrolyte ions,and facile charge transport for flexible wearable applications.The interconnected and compact electrode delivers a high volumetric capacitance(gravimetric capacitance)of 73 F cm−3(2446 F g−1),excellent rate capability,and cycle stability.The 3D-nickel cobalt-layered double hydroxide onto 3D-nickel wire(NiCo LDH/3D-Ni)//the 3D-manganese oxide onto 3D-nickel wire(Mn3O4/3D-Ni)hybrid supercapacitor exhibits energy density of 153.3 Wh kg−1 and power density of 8810 W kg−1.The red lightemitting diode powered by the as-prepared hybrid supercapacitor can operate for 80 min after being charged for tens of seconds and exhibit excellent electrochemical stability under various deformation conditions.The results verify that such wire-shaped 3D-hybrid supercapacitors are promising alternatives for batteries with long charge–discharge times,for smart wearable and implantable devices.     

用作双电层电容器电极材料的三维层次孔结构多孔炭的合成

以葡萄糖为碳源,由金属框架有机物( MOF)高效地合成出一种具有三维层次孔结构的多孔炭.当葡萄糖渗入到方形MOF的表面或内部空隙之后,逐步进行聚合和炭化.在此过程中,MOF分解出ZnO,ZnO进一步被基体炭或CO还原成Zn;而Zn又在炭化过程中逸出,以致形成连续的基体炭组织.当所合成的多孔炭用作双电层电容器电极材料时,在1 mo1/L NEt4 BF4/碳酸丙烯酯电解液体系中,其初始比电容达175F·g-1(电流强度0.6A·g-1),并在12A·g-1大电流密度下电容保持率高达94.2％.     

Nitrogen-doping hierarchically porous carbon nanosheets for supercapacitor

Two-dimensional (2D) porous carbon nanosheets attract great attention because of their thin sheet-like morphology, abundant pores and high specific surface area, and their potential applicability in many fields including adsorption, oxygen reduction reaction, organic transistor and energy storage. Herein, a feasible method, named self-templating, to prepare 2D nitrogen-doping hierarchically porous carbon nanosheets (N-HPCNs) with prominent performances as supercapacitor electrode is reported. During the process of preparation, the inexpensive and easily available MgO rods are treated in water to form Mg(OH)₂ nanosheets further using as templates and then nitrogen contained resorcinol–formaldehyde resin oligomers as carbon and nitrogen precursor co-condense onto the templates by electrostatic interaction. The obtained N-HPCNs with large specific surface area, hierarchical pores and unique interconnected sheet-like structure are the potential candidates for high energy storage devices. As an active electrode material for electrochemical double-layer capacitors, N-HPCNs exhibit a capacitance of 201 F g^?1 at current density of 1 A g^?1 and high specific capacitance (78.1% retention of initial capacitance even at 10 A g^?1), with excellent cycling life stability (3.5% loss after 5000 cycles).     

原位氧化法制备Zn-Ni氢氧化物纳米片及其电荷存储特性研究

通过简单、低成本的化学浴沉积法在泡沫镍上原位生成了Zn-Ni 氢氧化物(Zn-Ni double hydroxides)纳米片。SEM观察结果表明, Zn-Ni 氢氧化物纳米片均匀附着在泡沫镍表面, 形成均一的多孔纳米片阵列层。此外, 还有大量的Zn-Ni 氢氧化物纳米片聚集成多孔团聚体, 分布于泡沫镍骨架的空隙处, 从而获得较高的活性物质负载量(4.27 mg/cm²)。CV、CP和电化学阻抗测试表明, Zn-Ni 氢氧化物纳米片在2 mol/L KOH电解液中充放电电流密度1 A/g时, 比电容为746.2 F/g(面积电容为3.18 F/cm²); 3000次充放电循环后, 仍保持70.9%的初始比电容。     

自组装花状结构Ni(OH)2的微波水热合成与表征

以六水合硝酸镍为镍源,尿素为水解控制剂及聚乙二醇(PEG)为表面活性剂,采用微波水热法成功合成了由亚微米片自组装而成的花状结构Ni(OH)2,并通过进一步的热处理得到相同结构形貌的NiO.利用XRD、SEM、TEM、FTIR、UV-Vis等方法对产物进行了表征,结果表明,自组装花状结构Ni(0H)2的直径为2.5-4....