One-step synthesis of biomass derived O,N-codoped hierarchical porous carbon with high surface area for supercapacitors

We report a convenient method to synthesize O, N-codoped hierarchical porous carbon by one-step carbonization of the mixture of KHCO₃, urea and alginic acid. Benefiting from KHCO₃ and urea synergistic effect, the obtained O, N-codoped hierarchical porous carbon (NPC-700) material has a well-developed interconnected porous framework with ultrahigh specific surface area (2846 m²/g) and massive heteroatoms functional groups. Consequence, such porous carbon displays high specific capacitance (324 F/g at 1 A/g), excellent rate performance (212 F/g at 30 A/g) and good electrochemical stabilization in 6 mol/L KOH solution. More importantly, the assembled NPC-700//NPC-700 symmetrical supercapacitor can achieve a high energy density of 18.8 Wh/kg and good electrochemical stabilization in 1 mol/L Na₂SO₄ solution. This process opens up a new way to design heteroatoms-doped hierarchical porous carbon derived from biomass materials for supercapacitors.     

ZIF-derived mesoporous carbon materials prepared by activation via Na2SiO3 for supercapacitor

Metal organic frameworks (MOFs) derived carbonaceous materials have a wide range of applications in the fields of energy storage, catalysis, adsorption and separation, etc. Especially, zeolitic imidazolate framework-8 (ZIF-8) is an excellent candidate to synthesize porous carbon due to the large surface area and high nitrogen content. However, the dominated microporous structure of ZIF-8-derived carbon significantly hinders ionic mass transfer, limiting the improvement of performance. Herein, MOF-derived mesoporous carbon was prepared using ZIF-8 as carbon precursor and cheap sodium silicate (Na₂SiO₃) as activator. The introduction of Na₂SiO₃ created rich mesoporous structure and increased specific surface area, as well as the effects of pyrolysis temperature and Na₂SiO₃ dosage on performance was also investigated. The obtained ZIF-derived porous carbon exhibits good electrochemical performance with specific capacitance of 263 F/g at 1 A/g and excellent cycle life (96.07% after 10,000 GCD cycles) in supercapacitor. The use of cheap Na₂SiO₃ activator provides a new orientation for the preparation of MOF-derived carbons with rich pores, high surface area, and facilitates the large-scale application of MOF-derived carbons.     

Hierarchical porous carbon derived from coal-based carbon foam for high-performance supercapacitors

Hierarchical porous carbon (HPC) from bituminous coal was designed and synthesized through pyrolysis foaming and KOH activation. The obtained HPC (NCF-KOH) were characterized by a high specific surface area (S_BET) of 3472.41 m²/g, appropriate mesopores with V_mes/V_total of 57%, and a proper amount of surface oxygen content (10.03%). This NCF-KOH exhibited a high specific capacitance of 487 F/g at 1.0 A/g and a rate capability of 400 F/g at 50 A/g based on the three-electrode configuration. As an electrode for a symmetric capacitor, a specific capacitance of 299 F/g at 0.5 A/g was exhibited, and the specific capacitance retained 96% of the initial capacity at 5 A/g after 10,000 cycles. Furthermore, under the power density of 249.6 W/kg in 6 mol/L KOH, a high energy density of 10.34 Wh/kg was obtained. The excellent charge storage capability benefited from its interconnected hierarchical pore structure with high accessible surface area and the suitable amount of oxygen-containing functional groups. Thus, an effective strategy to synthesize HPC for high-performance supercapacitors serves as a promising way of converting coal into advanced carbon materials.     

Promising activated carbons derived from cabbage leaves and their application in high-performance supercapacitors electrodes

In this paper, cabbage leaves (CLs) were used to synthesize porous activated carbon by the carbonization and activation processes. The material for CLs were carbonized at 600 °C and activated at 800 °C with the KOH/C-600 mass ratio 4 (denoted as AC-800) show typical amorphous character and display porous structures with high specific surface areas 3102 m²/g via XRD and BET measurements. As the electro-active material, AC-800 electrode exhibit ideal capacitive behaviors in aqueous electrolytes and the maximal specific capacitance is as high as 336 F/g at the current density of 1 A/g. Furthermore, AC-800 electrode shows excellent electrochemical cycle stability with ～95 % initial capacitance being retained after 2000 cycles. The desirable capacitive performances enable the CLs to act as a new biomass source of carbonaceous materials for high-performance supercapacitors and low-cost electrical energy storage devices.     

N-doped honeycomb-like porous carbon towards high-performance supercapacitor

Biomass-derived porous carbon with developed pore structure is critical to achieving high performance electrode materials. In this work, we report a grape-based honeycomb-like porous carbon (GHPC) prepared by KOH activation and carbonization, followed by N-doping (NGHPC). The obtained NGHPC exhibits a unique honeycomb-like structure with hierarchically interconnected micro/mesopores, and high specific surface area of 1268 m²/g. As a supercapacitor electrode, the NGPHC electrode exhibits a remarkable specific capacitance of 275 F/g at 0.5 A/g in a three-electrode cell. Moreover, the NGHPC//NGHPC symmetric supercapacitor displays a high energy density of 12.6 Wh/kg, and excellent cycling stability of approximately 95.2% capacitance retention after 5000 cycles at 5 A/g. The excellent electrochemical performance of NGHPC is ascribed to its high specific surface area, honeycomb-like structure and high-content of pyrodinic-N (36.29%). It is believed that grape-based carbon materials show great potential as advanced electrode materials for supercapacitors.     

Lignin derived porous carbon with favorable mesoporous contributions for highly efficient ionic liquid-based supercapacitors

Lignin and its derivatives hold great potential in developing high performance porous carbon materials for supercapacitors due to the versatile features of high carbon content, abundant multifunctional groups, low cost, and environmental benefits. Unfortunately, their derived porous carbon generally has the features of unfavorable microporous-dominated morphologies and low specific surface area (SSA) attributed from the highly-branched structure of lignin, which are hardly suitable for the supercapacitors with ionic liquid (IL) electrolyte, leading to poor energy density and rate capability. Herein, porous carbon materials with desirable mesoporous contributions from sodium lignosulphonate are designed via a facile template method. Such rich mesoporisity carbon materials not only possess with three-dimensional interconnected network, large SSA, as well as favorable pore size distribution for accelerated ion and electron mass transfer, but also feature low heteroatom content for high electrochemical stability. Consequently, the optimal electrode exhibits a high capacitance of 166 F/g at 0.5 A/g, superior rate performance (59 Wh/kg at 59 kW/kg), as well as impressive cycle life with good capacitance retention of 93.1% in EMIBF₄ electrolytes. The present work opens a new avenue to design porous carbon materials with high mesopore properties from lignin for effective compatibility with IL electrolyte in high-performance supercapacitors.     

High-energy aqueous supercapacitors enabled by N/O codoped carbon nanosheets and “water-in-salt” electrolyte

A facile fabrication strategy is reported to obtain N/O codoped porous carbon nanosheets for purpose of ameliorating the charge transfer and accumulation in the concentrated Li TFSI(lithium bis（trifluoromethane sulfonyl）imide) electrolyte. By tunning the feed ratio of comonomers, the porous nanosheet structure is endowed with a significant ion-adsorption surface area（1630 m²/g） and interconnected hierarchical porosity; meanwhile, high-level N/O dopants（N: 3.58 at%, O: 12.91 at%） incre...     

Heteroatom‐Doped Porous Carbon Nanosheets: General Preparation and Enhanced Capacitive Properties

High‐performance electrical double‐layer capacitors (EDLCs) require carbon electrode materials with high specific surface area, short ion‐diffusion pathways, and outstanding electrical conductivity. Herein, a general approach combing the molten‐salt method and chemical activation to prepare N‐doped carbon nanosheets with high surface area (654 m² g^?1) and adjustable porous structure is presented. Owing to their structural features, the N‐doped carbon nanosheets exhibited superior capacitive performance, demonstrated by a maximum capacitance of 243 F g^?1 (area‐normalized capacitance up to 37 μF cm^?2) at a current density of 0.5 A g^?1 in aqueous electrolyte, high rate capability (179 F g^?1 at 20 A g^?1), and excellent cycle stability. This method provides a new route to prepare porous and heteroatom‐doped carbon nanosheets for high‐performance EDLCs, which could also be extended to other polymer precursors and even waste biomass.     

Sub-nanopores-containing N,O-codoped porous carbon from molecular-scale networked polymer hydrogel for solid-state supercapacitor

A template-free carbonization-activation route is developed to fabricate sub-nanopore-containing porous carbon by using a novel polypyrrole(PPy) hydrogel as a precursor.This design of PPy hydrogel precursor containing molecular-scale grids(diameter～2.0 nm) allows for homogeneous N,O-codoping into the porous carbon scaffold during the pyrolysis process.A subsequent activation step produces activated porous carbons(APCs) with tailored pore structures,which renders the APCs abundant subnanopores on their surface to increase the specific capacitance as extra capacitance sites.Coupled with large specific surface area and abundant heteroatoms,the optimized APC4/1 displays excellent specific capacitance of 379 F/g for liquid-state supercapacitor and 230 F/g for solid-state supercapacitor.The solid-state supercapacitor shows a high energy density of 22.99 Wh/kg at power density of 420 W/kg,which is higher than most reported porous carbon materials and satisfy the urgent requirements of elementary power source for electric vehicles.Moreover,this method can be easily modified to fabricate sub-nanopore-containing porous carbons with preferred structures and compositions for many applications.     

萘基相互连接的多孔碳纳米囊的制备及超电容性能

以萘为碳源, 采用MgO模板诱导耦合KOH裁剪技术制备了相互连接的多孔碳纳米囊(ICNC). 结果表明所制备的ICNC₂具有大的比表面积(1811 m²/g)、 高的压实密度(1.38 g/cm³)和微孔孔容含量(58.93%). 在对称的超级电容器(SC)中, ICNC₂电极的体积比容在不同电流密度下分别高达420.8 F/cm³(0.069 A/cm³)和315 F/cm³(27.6 A/cm³), 容量保持率为74.82%. 在38 W/L功率密度下, ICNC₂基SC的体积能量密度为14.6 W?h/L. 经过20000次循环后, 其体积比容仅衰减1.4%, 库伦效率为99.1%, 为从萘基小分子制备储能用功能碳材料提供了一种可行的方法.     

In Situ Growth of MnO2 Nanosheets on N‐Doped Carbon Nanotubes Derived from Polypyrrole Tubes for Supercapacitors

Nitrogen‐doped porous carbon nanotubes@MnO₂ (N‐CNTs@MnO₂) nanocomposites are prepared through the in situ growth of MnO₂ nanosheets on N‐CNTs derived from polypyrrole nanotubes (PNTs). Benefiting from the synergistic effects between N‐CNTs (high conductivity and N doping level) and MnO₂ nanosheets (high theoretical capacity), the as‐prepared N‐CNTs@MnO₂‐800 nanocomposites show a specific capacitance of 219 F g^?1 at a current density of 1.0 A g^?1, which is higher than that of pure MnO₂ nanosheets (128 F g^?1) and PNTs (42 F g^?1) in 0.5 m Na₂SO₄ solution. Meanwhile, the capacitance retention of 86.8 % (after 1000 cycles at 10 A g^?1) indicates an excellent electrochemical performance of N‐CNTs@MnO₂ prepared in this work.     

Humic acid‐derived hierarchical porous carbon preparation using vacuum freeze‐drying for electric double layer capacitors

Electric double layer capacitors (EDLCs) preserve charge by reversible physisorption of electrolyte ions on the surface of porous active materials. Therefore, engineering a reasonable pore structure and reducing oxygen‐containing groups of carbon materials are efficient approaches to enable rapid ion diffusion pathways and long life span, respectively. Here, humic acid (HA)‐derived hierarchical porous carbon was fabricated by vacuum freeze‐drying, KOH activation, and subsequent annealing. The macropores were generated from the vacancies where the ice crystals in the HA–KOH gels initially occupied during vacuum‐freeze drying, while abundant micropores were created from homogeneous KOH activation. In addition, subsequent annealing further reduced the oxygen‐containing groups. When used as EDLC electrodes in 1 mol/L TEABF₄/PC organic electrolyte, they could give a high capacitance of 150 F/g at 0.05 A/g and excellent rate performance of 81% (with capacitance of 121.46 F/g at 10 A/g). More importantly, the hierarchical porous carbon displays superior capacity retention of 85.6% after 10,000 cycles at 1 A/g at 2.7 V.     

Preparation of nitrogen doped clews-like carbon materials and their application as the electrode in supercapacitor

Nitrogen doped clews-like hierarchical porous carbon materials, fabricated by means of a one-pot hydrothermal reaction and post treatment, exhibit superior supercapacitive performances.     

Asymmetric supercapacitors based on stabilized α-Ni(OH)2 and activated carbon

In this work, stabilized Al-substituted α-Ni(OH)₂ materials were successfully synthesized by a chemical coprecipitation method. The experimental results showed that the 7.5% Al-substituted α-Ni(OH)₂ materials exhibited high specific capacitance (2.08?×?10³ F/g) and excellent rate capability due to the high stability of Al-substituted α-Ni(OH)₂ structures in alkaline media, suggesting its potential application in electrode material for supercapacitors. To enhance energy density, an asymmetric type pseudo/electric double-layer capacitor was considered where α-Ni(OH)₂ materials and activated carbon act as the positive and negative electrodes, respectively. Values for the maximum specific capacitance of 127 F/g and specific energy of 42 W·h/kg were demonstrated for a cell voltage between 0.4 and 1.6 V. By using the α-Ni(OH)₂ electrode, the asymmetric supercapacitor exhibited high energy density and stable power characteristics. The hybrid supercapacitor also exhibited a good electrochemical stability with 82% of the initial capacitance over consecutive 1,000 cycle numbers.     

The production of activated carbon from cation exchange resin for high-performance supercapacitor

High-performance activated carbon for electrochemical double-layer capacitors (EDLC) has been prepared from cation exchange resin by carbonization and subsequent activation with KOH. The activation temperature has a key role in the determination of porous carbon possessing high surface areas, and large pore structures. The porous carbon activated at 700 °C (carbon-700-1:4) has high surface area (2236 m²?g^?1) and large total pore volume (1.15 cm³?g^?1), which also displays best capacitive performances due to its well-balanced micro- or mesoporosity distribution. In details, specific capacitances of the carbon-700-1:4 sample are 336.5 F?g^?1 at a current density of 1 A?g^?1 and 331.8 F?g^?1 at 2 A?g^?1. At high current density as 20 A?g^?1, the retention of its specific capacitance is 68.4 %. The carbon-700-1:4 sample also exhibits high performance of energy density (46.7 Wh?kg^?1) and long cycle stability (～8.9 % loss after 3,000 cycles). More importantly, due to the amount of waste ion-exchange resins increasing all over the world, the present synthetic method might be adopted to dispose them, producing high-performance porous carbons for EDLC electrode materials.     

氮掺杂石墨烯量子点/MOF衍生多孔碳纳米片构筑高性能超级电容器

首先采用溶液法在碳布上生长Co-MOF二维纳米片,通过高温退火和刻蚀后得到MOF衍生多孔碳纳米片。以Co-MOF衍生的多孔碳纳米片/碳布(CNS/CC)作为碳基骨架,采用电化学沉积法负载高活性氮掺杂石墨烯量子点(N-GQDs),制备得到分级多孔结构的N-GQD/CNS/CC复合材料。组装成自支撑且无粘结剂的N-GQD/CNS/CC电极,当电流密度为1 A·g~(-1)时,其比电容高达423 F·g~(-1)。通过储能机制和电容贡献机制的研究表明,在碳纤维上原位生长的具有高双电层电容的CNS和表面负载具有高赝电容的N-GQDs之间相互协同作用,使得N-GQD/CNS/CC电极具有高电容性能,是一种理想的超级电容器电极材料。电极材料的高导电、分级多孔结构有利于电子的传输和电解质离子的扩散,具有良好的动力学性能,能快速充放电和具有优异的倍率特性。将电极组装成对称型超级电容器,功率密度为250 W·kg~(-1)时对应的能量密度达到7.9 Wh·kg~(-1),且经过10 000次循环后电容保持率为91.2%,说明氮掺杂石墨烯量子点/MOF衍生多孔碳纳米片复合材料是一种电化学性能稳定的具有高电容性能的全碳电极材料。     

纤维素纳米晶模板法制备多级孔炭材料及其电化学性能

以纤维素纳米晶(CNC)为模板,酚醛树脂为碳源,KOH为活化剂,通过高温碳化制备了多级孔炭材料.采用透射电子显微镜(TEM)、扫描电子显微镜(SEM)和X射线光电子能谱仪(XPS)等手段对合成的一系列炭材料进行了表征.结果表明,前驱体中CNC的降解会形成与CNC直径相当的介孔,KOH活化则会导致炭材料产生大量的微孔和大孔,以及部分4 nm左右较小尺度的介孔,所制备炭材料呈现明显的多级孔特性,其比表面积达554.7 m²/g,总孔体积为0.323 cm³/g.以CNC为模板,KOH活化的炭材料作为电极材料时,在1.0 A/g电流密度下其比电容达202.8 F/g,当电流密度升高至40.0 A/g时,其电容保持率仍达69%,表明该炭材料具有优异的倍率性能;由该电极材料组装的超级电容器在10000次充放电循环后,电容保持率达95%以上,具有良好的循环稳定性.     

Development of the Self-doping Porous Carbon and Its Application in Supercapacitor Electrode

The massive discharge of biomass wastes not only causes waste of resources, but also pollutes the environment. Therefore, converting biomass wastes into carbon materials is an effective way to solve the above problems. Here, using biomass waste pig nails as raw materials and K₂CO₃ as chemical activators, the N-doped porous carbon(KPNC) is prepared by direct pyrolysis. As an electrode for supercapacitors, the electrochemical tests of KPNCs showed that they exhibited good electrochemical performance and excellent cycling stability. When the current density is 0.2 A/g, the specific capacitance is up to 344.6 F/g. Moreover, it still maintains 97.6% initial capacitance retention after 2000 cycles at a high current density of 5 A/g. Above exceptional electrochemical performances may be ascribed to an appropriate porous structure(S_micro/S_total=80.31%, V_micro/V_total=76.19%), high nitrogen contents(4.44%, atomic fraction), oxygen contents(9.13%, atomic fraction) as well as small internal resistance. The above experimental results show that the conversion of pig nails to porous carbon can reduce the waste of resources and alleviate environmental pollution.     

掺氮介孔炭作为双功能材料用于氧还原与超级电容器

以壳聚糖为含氮碳源,正硅酸乙酯为软模板,硝酸镍为催化剂,通过简单的低温水热法及后续炭化,成功合成出掺氮介孔炭材料（NMC-1）.NMC-1含有多孔结构以及氮氧等杂原子,能提高其电催化性能、双电层电容与赝电容.由于NMC-1在碱液中表现出显著的催化氧还原反应活性和具有较高的超级电容器比电容（在0.2A/g时为252F/g）及好的循环稳定性,因此,它有可能作为一种可再生、环保的双功能材料同时应用于燃料电池与超级电容器领域.     

Hierarchical porous nanofibers of carbon@nickel oxide nanoparticles derived from polymer/block copolymer system

The triblock copolymer (PAA-b-PAN-b-PAA) is prepared by reversible addition-fragmentation chain-transfer polymerization, and then blended with polymer (PAN) and metal hydroxide (Ni(OH)₂) as a precursor for heat-treatment. A composite material of hierarchical porous nanofibers and nickel oxide nanoparticles (HPCF@NiO) is prepared by electrospinning combined with high-temperature carbonization. The effects of the ratio of PAA and PAA-b-PAN-b-PAA on the internal structure of nanofibers and their electrochemical properties as positive electrode materials are investigated. The experimental results show that when the ratio of PAA to PAA-b-PAN-b-PAA is 1.3 to 0.4, it has good pore structure and excellent electrochemical performance. At the current density of 1 A/g, the specific capacitance is 188.7 F/g and the potential window is −1 V to 0.37 V. The asymmetric supercapacitor assembled with activated carbon as the negative electrode materials has a specific capacitance of 21.2 F/g in 2 mol/L KOH and a capacitance retention of 85.7% after 12,500 cycles at different current density.