Layer-by-layer engineered Co-Al hydroxide nanosheets/graphene multilayer films as flexible electrode for supercapacitor

Multilayer films of Co-Al layered double hydroxide nanosheets (Co-Al LDH-NS) and graphene oxide (GO) were fabricated through layer-by-layer (LBL) assembly. By using a three-electrode system, the electrochemical performances of the films were investigated to evaluate their potential as electrode materials to be used in flexible supercapacitor devices. The Co-Al LDH-NS/GO multilayer films exhibited a high specific capacitance of 880 F/g and area capacitance of 70 F/m(2) under the scan rate of 5 mV/s. And the film exhibited good cycle stability over 2000 cycles. After treating the films at 200 °C in H(2) atmosphere, the specific capacitance and area capacitance were largely increased up to 1204 F/g and 90 F/m(2) due to partial reduction of GO. A flexible electrode by depositing Co-Al LDH-NS/GO multilayer film onto PET substrate was prepared to show the potential of Co-Al LDH-NS/GO films for flexible energy storage.     

离子液体电解质种类对活性炭电极超级电容器电化学性能的影响

本文将经水蒸气二次活化的椰壳活性炭（W-AC）作为电极材料,选择1-乙基-3甲基咪唑四氟硼酸盐（[EMIM]BF₄）作为电解质,结果表明W-AC电极的比电容量远高于未活化的椰壳活性炭（R-AC）.使用循环伏安、恒电流充放电、交流阻抗等方法研究了不同种类离子液体电解质对超级电容器电化学性能的影响.不同阴阳离子组成的离子液体作为电解质,直接影响超级电容器的电化学性能. 研究表明,由EMIM⁺和BMIM⁺阳离子与BF₄^-、TFSI^-阴离子构成的离子液体电解质较适用于W-AC电极. 其中在[EMIM]BF₄电解质中,单片电极的比电容量可高达153 F·g^-1;在1-丁基-3-甲基-咪唑四氟硼酸盐（[BMIM]BF₄）电解质中电位窗可达3.5V,能量密度可高达57 Wh·kg^-1.本研究对于构筑高性能超级电容器离子液体的选择提供参考,以满足不同应用领域需求.     

高容量超级电容器电极材料的设计与制备

超级电容器寿命长,安全性高,并可以实现快速充放电,是化学电源研究的热点之一。然而,超级电容器的能量密度较低限制了其更多的应用。因此,超级电容器领域的研究关注点在如何提高超级电容器的能量密度。其中,提高比容量是提高能量密度的一种有效途径。本文通过对电极材料和电解液的优化来研究制备得到高容量超级电容器的方法。电极材料的比表面积、孔道结构和导电性对其电化学性能有着直接的影响。一方面,通过优化电极材料的孔道结构和比表面积可以增加活性位点并提高电解液离子传导率,从而得到高比电容。另一方面,电极材料导电性的提高有利于提升其电子传导率从而得到较高的比容量。本文分别对碳材料和金属氧化物/氢氧化物的优化达到了增加双电层电容和赝电容的目的。不仅如此,还可以通过在电解液中增加氧化还原电对从而得到高比电容。这一方法为高容量超级电容器的制备提供了新的思路。     

Synthesis of Co3O4/CoOOH via electrochemical dispersion using a pulse alternating current method for lithium-ion batteries and supercapacitors

We report a convenient, low-cost and ecofriendly approach for the fabrication of a Co₃O₄/CoOOH electrode material intended for lithium ion batteries (LIBs) and supercapacitors (SCs) using the electrochemical dispersion of the cobalt foil through the pulse alternating current (PAC) method. The synthesized material is a Co₃O₄/CoOOH composite (with about 10–15 wt% CoOOH) in the form of nanosheets with a length of approximately 200 nm and a thickness of 10–20 nm. It is found to exhibit high reversible discharge specific capacities and good cycling behavior while tested as the anode material in LIBs. Measuring the reversible capacitance at high (2C) and low (C/20) cycling rates gives the values of 610 mAh g⁻¹ and 1030 mAh g⁻¹, respectively. The specimen possesses excellent performance as the electrode for SCs with the retention of capacitance up to 98% at the current density increasing from 0.5 to 10 A g⁻¹. After 1000 cycles at a current density of 10 A g⁻¹ the electrode maintains about 90% of its initial capacitance which evidences the long cycle life. Hence, electrochemically prepared Co₃O₄/CoOOH seems to be a promising candidate for high-performance LIBs and SCs applications.     

基于NiCo2O4纳米片电极的非对称混合电容器

The looming global energy crisis and ever-increasing energy demands have catalyzed the development of renewable energy storage systems. In this regard, supercapacitors (SCs) have attracted widespread attention because of their advantageous attributes such as high power density, excellent cycle stability, and environmental friendliness. However, SCs exhibit low energy density and it is important to optimize electrode materials to improve the overall performance of these devices. Among the various electrode materials available, spinel nickel cobaltate (NiCo₂O₄) is particularly interesting because of its excellent theoretical capacitance. Based on the understanding that the performances of the electrode materials strongly depend on their morphologies and structures, in this study, we successfully synthesized NiCo₂O₄ nanosheets on Ni foam via a simple hydrothermal route followed by calcination. The structures and morphologies of the as-synthesized products were characterized by X-ray diffraction, scanning electron microscopy, and Brunauer-Emmett-Teller (BET) surface area analysis, and the results showed that they were uniformly distributed on the Ni foam support. The surface chemical states of the elements in the samples were identified by X-ray photoelectron spectroscopy. The as-synthesized NiCo₂O₄ products were then tested as cathode materials for supercapacitors in a traditional three-electrode system. The electrochemical performances of the NiCo₂O₄ electrode materials were studied and the area capacitance was found to be 1.26 C·cm^-2 at a current density of 1 mA·cm^-2. Furthermore, outstanding cycling stability with 97.6% retention of the initial discharge capacitance after 10000 cycles and excellent rate performance (67.5% capacitance retention with the current density from 1 to 14 mA·cm^-2) were achieved. It was found that the Ni foam supporting the NiCo₂O₄ nanosheets increased the conductivity of the electrode materials. However, it is worth noting that the contribution of nickel foam to the areal capacitance of the electrode materials was almost zero during the charge and discharge processes. To further investigate the practical application of the as-synthesized NiCo₂O₄ nanosheets-based electrode, a device was assembled with the as-prepared samples as the positive electrode and active carbon (AC) as the negative electrode. The assembled supercapacitor showed energy densities of 0.14 and 0.09 Wh·cm^-3 at 1.56 and 4.5 W·cm^-3, respectively. Furthermore, it was able to maintain 95% of its initial specific capacitance after 10000 cycles. The excellent electrochemical performance of the NiCo₂O₄ nanosheets could be ascribed to their unique spatial structure composed of interconnected ultrathin nanosheets, which facilitated electron transportation and ion penetration, suggesting their potential applications as electrode materials for high performance supercapacitors. The present synthetic route can be extended to other ternary transition metal oxides/sulfides for future energy storage devices and systems.     

High Energy Density Heteroatom (O,N and S) Enriched Activated Carbon for Rational Design of Symmetric Supercapacitors

Carbon-based symmetric supercapacitors (SCs) are known for their high power density and long cyclability, making them an ideal candidate for power sources in new-generation electronic devices. To boost their electrochemical performances, deriving activated carbon doped with heteroatoms such as N, O, and S are highly desirable for increasing the specific capacitance. In this regard, activated carbon (AC) self-doped with heteroatoms is directly derived from bio-waste (lima-bean shell) using different KOH activation processes. The heteroatom-enriched AC synthesized using a pretreated carbon-to-KOH ratio of 1:2 (ONS@AC-2) shows excellent surface morphology with a large surface area of 1508 m² g⁻¹. As an SC electrode material, the presence of heteroatoms (N and S) reduces the interfacial charge-transfer resistance and increases the ion-accessible surface area, which inherently provides additional pseudocapacitance. The ONS@AC-2 electrode attains a maximum specific capacitance (C_sp) of 342 F g⁻¹ at a specific current of 1 Ag⁻¹ in 1 m NaClO₄ electrolyte at the wide potential window of 1.8 V. Moreover, as symmetric SCs the ONS@AC-2 electrode delivers a maximum specific capacitance (C_sc) of 191 F g⁻¹ with a maximum specific energy of 21.48 Wh kg⁻¹ and high specific power of 14 000 W kg⁻¹ and excellent retention of its initial capacitance (98 %) even after 10000 charge/discharge cycles. In addition, a flexible supercapacitor fabricated utilizing ONS@AC-2 electrodes and a LiCl/polyvinyl alcohol (PVA)-based polymer electrolyte shows a maximum C_sc of 119 F g⁻¹ with considerable specific energy and power.     

活性炭二次活化对其电化学容量的影响

为进一步提高作为电化学超级电容器电极材料活性炭的电化学容量, 采用KOH作为二次活性剂, 将所得活性炭进行二次化学活化处理, 从而得到二次活化活性炭. 将原始活性炭材料与二次活化活性炭材料都分别经过系列处理, 组装成电化学超级电容器进行电化学性能测试. 测试结果表明, 二次活化活性炭材料的电化学容量达到145.0 F·g-1(有机电解液), 远远大于原活性炭材料的容量(45.0 F·g-1). 为研究二次活化活性炭材料电化学容量大幅提高的原因, 将这两种材料分别进行微观结构数据测试, 包括比表面积、N2吸脱附等温曲线和孔径分布. 研究结果表明, 二次活化处理大大增加了二次活化活性炭材料在孔径为2-3 nm的中孔分布, 从而证实对于有机电解液, 电极材料在2-3 nm的中孔对其电化学容量的提高具有重要意义.     

High-capacity porous carbons prepared by KOH activation of activated carbon for supercapacitors

High-performance supercapacitor electrode materials are prepared from the commercially available activated carbon （AC） through a facile and low-cost chemical activation method. The obtained results show that AC activated by KOH with an alkali/carbon ratio of 6/1 （ACK6） possesses a specific surface area of 3405 m^2/g, a large pore volume of 2.01 cm^3/g, and exhibits the highest initial specific capacitance of 335 F/g at the current density of 0.5 A/g in 6 mol/L KOH, and 85% coloumbic efficiency for 5000 cycles at 20 mV/s.     

High performance pliable supercapacitor fabricated using activated carbon nanospheres intercalated into boron nitride nanoplates by pulsed laser ablation technique

Pliable supercapacitor, yielding specific capacitance (C_s) and energy density as high as 348 F g⁻¹ and 48.3 Wh Kg⁻¹ respectively was fabricated using modified activated carbon electrodes. The nanospheres of activated carbon (AC) were anchored on the nanoplates of boron nitride (BN) by employing the facile technique of pulsed laser ablation in liquid (PLAL) using 532 nm focused laser beam. Four different variants of electrode materials were synthesized by varying the weight percentage (1%, 3%, 5% and 10%) of BN in AC in the PLAL precursor solution. The morphological characteristics, the elemental composition and the structural analysis of the synthesized electrode materials were studied respectively by FESEM, XPS and XRD. The morphological studies indicated that the PLAL synthesis of the electrode materials resulted in proper intercalation of carbon nanospheres into BN nanoplates, which resulted in the observed enhanced performance of the fabricated supercapacitor. Four supercapacitors in this work were fabricated using the four variants of synthesized electrode materials in conjunction with gel polymer electrolyte (GPE). GPE are well known for their non-corrosive nature and best sealing ability to avoid any leakage that results in increasing the cycle life of the device. The performance of the fabricated supercapacitors was evaluated using cyclic voltammetry (CV), galvanostatic charge discharge (GCD) measurement and electrochemical impedance spectroscopy (EIS). The results indicate that the supercapacitor fabricated using 3% BN in AC as electrode material manifested the best specific capacitance and energy density. Also it was found that the supercapacitor maintained 85% of its initial capacitance even after 5000 charge/discharge cycles.     

Highly Stretchable and Conductive Hybrid Fibers for High-performance Fibrous Electrodes and All-solid-state Supercapacitors

The development of lightweight, flexible, and stretchable energy storage systems is essential for state-of-the-art electronic devices.We propose a new and broad strategy to fabricate a stretchable and conductive GO/CNTs-TPU fiber electrode by direct wet spinning, from which a flexible fibrous supercapacitor is fabricated. The fibrous electrode exhibits a high strength of 11.68 MPa, high conductivity of 342 S/cm, and high specific capacitances(21.8 mF/cm, 36.45 F/cm~3, and 95 F/g). The specific capacitance of the assembled all-solid-state hybrid fiber-shaped supercapacitor reaches 14.3 F/cm~3. After 5000 charge-discharge cycles, 97% of the capacitance of the hybrid supercapacitor is maintained. These high-strength electrochemical electrode materials could be potential candidates for applications in practical and large-scale energy storage systems and textile clothes.     

掺钇纳米NiO的制备及其超大电容性能研究

应用化学共沉淀法制备掺Y的纳米N iO.XRD分析表明,Y的添加不改变N iO的晶体结构,但晶粒尺寸有所减小.利用恒流充放电、循环伏安和交流阻抗等测试方法对Y-N iO电极材料在5 mo.lL-1KOH溶液中作电化学性能测试.结果表明,化学掺杂提高了电极的比容量,当N iO与Y2O3的质量比为1∶0.1时,单电极放电比容量可达到363 F.g-1,比纯氧化镍电极提高了2.02倍.交流阻抗测试显示,Y掺杂降低了电解液在电极中的扩散阻力,提高了质子扩散能力,从而表现了更好的电容性能.     

Ultrafast room-temperature reduction of graphene oxide by sodium borohydride,sodium molybdate and hydrochloric acid

Since graphene-based materials have shown great potential in many fields,it is important to explore ultrafast and high-efficient methods to synthesize reduced graphene oxide(rGO) using inexpensive reducing agents under mild conditions.Here,we reported a novel method for the ultrafast chemical reduction of graphene oxide(GO) at room temperature using sodium borohydride(NaBH₄),sodium molybdate(Na₂MoO₄) and hydrochloric acid(HCl).The reduction was carried out within 2 min.A series of characterization results revealed that the obtained reduced graphene oxide has higher reduction degree than that synthesized by NaBH₄ alone at high temperature.Moreover,rGO electrode based on the present reducing method exhibited a superior specific capacitance of 139.8 F/g at a current density of1 A/g,indicating that it can be used as electrode materials for supercapacitors.     

Facile synthesis of high electrical conductive CoP via solid-state synthetic routes for supercapacitors

Co-P precursor was prepared by a mechanical alloying method and then is controlled to synthesis of Co P phase through an annealing method. The optimal conditions of ball milling and annealing temperature are investigated. The Co P exhibits higher electrical conductivity than graphite and cobalt oxide, showing excellent pseudocapacitive properties due its high electrical conductivity which can result in a fast electron transfer in high rate charge–discharge possess. The as-obtained Co P electrode achieves a high specific capacitance of 447.5 F/g at 1 A/g, and displays an excellent rate capability as well as good cycling stability. Besides, the asymmetric supercapacitor(ASC) based on the Co P as the positive electrode and activated carbon(AC) as the negative electrode was assembled and displayed a high rate capability(60%of the capacitance is retained when the current density increased from 1 A/g to 12 A/g), excellent cycling stability(96.7% of the initial capacitance is retained after 5000 cycles), and a superior specific energy of19 Wh/kg at a power density of 350.8 W/kg. The results suggest that the Co P electrode materials have a great potential for developing high-performance electrochemical energy storage devices.     

Three-dimensional paper-like graphene framework with highly orientated laminar structure as binder-free supercapacitor electrode

A free-standing paper-like three-dimensional graphene framework(3DGF) with orientated laminar structure and interconnected macropores, was obtained by the hard template-directed ordered assembly. As the sacrificial templates, polystyrene(PS) latex spheres were assembled with graphene oxide(GO) to build up a sandwich type composite film, followed by heat removal of which with a simultaneous reduction of GO. The 3DGF exhibited high specific surface area of 402.5 m2/g, controllable pores and mechanical flexibility, which was employed as the binder-free supercapacitor electrode and shows high specific gravimetric capacitance of 95 F/g at 0.5 A/g, with enhanced rate capability in 3 electrode KOH system.     

Electrodeposited NiSe_2 on carbon fiber cloth as a flexible electrode for high-performance supercapacitors

A flexible electrode of nickel diselenide/carbon fiber cloth(NiSe_2/CFC) is fabricated at room temperature by a simple and efficient electrodeposition method. Owing to NiSe_2 character of nanostructure and high conductivity, the as-synthesized electrodes possess perfect pseudocapacitive property with high specific capacitance and excellent rate capability. In three-electrode system, the electrode specific capacitance of the NiSe_2/CFC electrode varies from 1058 F g~(-1) to 996.3 F g~(-1) at 2 A g~(-1) to 10 A g~(-1) respectively, which shows great rate capability. Moreover, the NiSe_2 electrode is assembled with an active carbon(AC) electrode to form an asymmetric supercapacitor with an extended potential window of 1.6 V. The asymmetric supercapacitor possesses an excellent energy density 32.7 Wh kg~(-1) with a power density 800 W kg~(-1) at the current density of 1 A g~(-1). The nanosheet array on carbon fiber cloth with high flexibility, specific capacitance and rate capacitance render the NiSe_2 to be regarded as the promising material for the high performance superconductor.     

高性能碳基与过渡金属化合物基超级电容器电极材料的研究进展

超级电容器因其在电动车和便携式设备上巨大的应用潜力而受到广泛关注. 电极材料是超级电容器的关键组成部分, 决定了超级电容器性能的好坏. 近来大量研究以碳材料和过渡金属化合物作为电极材料. 然而, 碳材料电容值极小与过渡金属化合物导电性和稳定性差, 极大地限制了它们在超级电容器中的应用. 本综述重点介绍了我们课题组近年来在设计、可控制备及优化碳材料与过渡金属氧/氮化物电容性能的相关研究工作, 并讨论了材料构效关系及其调控机理. 最后对碳材料和过渡金属化合物作为电极材料的日后研究进行了展望.     

Layered silicate magadiite–derived three-dimensional honeycomb-like cobalt–nickel silicates as excellent cathode for hybrid supercapacitors

Developing low-cost electrode materials with high performance is the priority among priorities for large-scale application of supercapacitors (SCs). Magadiite, the most ubiquitous material on Earth, is half-abandoned and half-forgotten, and it is extremely valuable for development to useful materials, such as ‘a potential stock’ to be developed. Herein, we conceive the transformation of magadiite to electrode materials, pursuing the aim ‘waste can be turned into treasure’. Fortunately, three-dimensional honeycomb-like cobalt–nickel silicate (Co_xNi_2-xSiO₄) as high-performance electrode material for SCs is achieved via two simple steps of exfoliation and hydrothermal process. The bimetallic synergistic effect derived from Co/Ni can improve the reactivity of the material, and the honeycomb-like morphology can facilitate ion migration, so the electrochemical properties are enhanced. As a consequence, the Co_xNi_2-xSiO₄ electrode exhibited a specific capacitance of 1,097 F/g (548 C/g) at 0.5 A/g, as well as excellent cyclic stability of 101% retention after 10,000 cycles. The hybrid SC device is assembled by Co_xNi_2-xSiO₄ and active carbon (Co_xNi_2-xSiO₄//AC), and it delivers an excellent energy density of 15.5 Wh/m² at a power density of 1.34 W/m² and cycling stability (100% after 10,000 cycles). This work not only realizes the transformation of magadiite to transition metal silicates (TMSs) as electrode materials for high-performance SCs but also broadens the application of magadiite and opens up a novel strategy for synthesizing TMSs.     

Electrochemical Investigation of Activated Carbon Electrode Supercapacitors

Supercapacitors, also called as ultracapacitors, are electrochemical energy-storage devices that exploit the electrostatic interaction between high-surface-area nanoporous electrodes and electrolyte ions, combining properties of conventional batteries and conventional capacitors. A symmetrical activated carbon (AC) electrode supercapacitor has been fabricated in a simple and inexpensive manner. The AC has been synthesized from Charcoal, has activated in a furnace at high temperatures. The electrode was fabricated by casting slurry made of AC and blended in a polymer solution on the counter electrode (current collector), appeared to have high mechanical strength. The electrochemical performance of the prepared samples was tested in 1 M KCl solution by cyclic voltammetry (CV), galvanostatic charge discharge technique, and impedance spectroscopy. The surface and cross-section of electrode was observed with SEM. Capacitance of fabricated supercapacitor has a favorable capacitance in the range of 65–70 F/g with low resistance. The AC electrode supercapacitor has excellent electro chemical reversibility, good cycle stability with a low fading rate of specific capacitance even after 500 cycles, which is promising for energy storage applications.     

氧化锰表面改性活性炭电极材料的电化学特性

用Mn(NO3)2溶液浸渍-高温热解法对普通活性炭进行表面改性处理以改善其电化学性能. 采用氮气吸附、SEM、XRD等方法研究改性活性炭的比表面积、孔结构、形貌和氧化锰的晶体结构; 用循环伏安、恒流充放电、交流阻抗等电化学方法研究了改性活性炭电极构成的电化学电容器的性能. 结果表明, Mn(NO3)2热解产生的多价态氧化锰有法拉第赝电容效应, 尤其是立方晶形结构的α-Mn2O3, 与活性炭的双电层电容构成了复合电容, 因而改性炭材料的比电容有明显的提高, 其质量比电容达到254 F·g-1, 比未改性炭的165 F·g-1提高了54%. 改性炭电极电化学电容器具有优异的充放电可逆性和稳定性, 而且等效串联电阻较小, 只有0.40 Ω; 经2000次循环的长期测试, 容量保持率几乎达到100%.     

高能量密度和功率密度炭电极材料

以核桃壳为原料, 采用同步物理-化学活化法制备活性炭(AC). 用氮气吸附法和傅立叶红外光谱(FTIR), 对活性炭的孔结构和表面官能团进行了分析. 以活性炭为电极材料制备炭电极, 6 mol·L-1 KOH溶液为电解液组装成超级电容器, 利用恒电流充放电、循环伏安、交流阻抗等电化学测试方法研究其电化学性能及其与活性炭材料结构的关系. 结果表明, 实验电容器的内电阻、漏电流小, 循环充放电稳定性好, 容量保持率高; 活性炭的比电容随比表面积的增加而增大, 且与BET比表面积呈线性相关; 孔径在1.5-4 nm之间的孔表面有利于形成有效的双电层. 中等比表面积1197 m2·g-1炭样的比电容高达292 F·g-1, 80 mA充放电时, 电容器能量密度高达7.3 Wh·kg-1, 功率密度超过770 W·kg-1,峰值功率密度为5.1 W·g-1.