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.     

Effect of removing silica in rice husk for the preparation of activated carbon for supercapacitor applications

The significant influence of silica inside rice husk in the preparation and electrochemical performances of activated carbon are investigated. The removing of silica results in high mesoporous ratio and good rate capability.     

基于聚多巴胺的氮掺杂碳材料的制备及其电化学性能

多孔碳材料由于高的比表面积、优异的电子传导率、良好的化学稳定性等优点在超级电容器电极材料领域被广泛研究。 碳材料的组成及表面孔结构直接影响其电化学性能,为进一步提高碳材料的电容性能,本文首次以聚多巴胺球为前体,KOH为活化剂,通过高温碳化成功制备了良好电化学性能的氮掺杂多孔碳材料。 通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、 X射线粉末衍射(XRD)、傅里叶变换红外光谱(FT-IR)、X射线光电子能谱(XPS)和Raman光谱等对所制备的氮掺杂多孔碳材料进行了形貌及结构组成的表征。 在6 mol/L KOH电解液中, 采用循环伏安、恒电流充放电对多孔碳材料的电化学性能进行了研究。 结果表明,由于双电层电容和赝电容的协同作用,在电流密度为1 A/g时,材料的比电容可达269 F/g,充放电循环1000圈后电容仍可保留初始值的93.5%。     

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.     

KOH Direct Activation for Preparing Activated Carbon Fiber from Polyacrylonitrile-based Pre-oxidized Fiber

The activated carbon fiber（ACF） was prepared from polyacrylonitrile-based pre-oxidized fiber（PANOF） by KOH direct activation. The influence of activation conditions including impregnation ratio（the mass ratio of PANOF to KOH）, activation temperature and activation time on the pore structure and electrochemical properties of ACF was investigated, and the corresponding activation mechanism was proposed. The ACF prepared at an activation temperature of 800℃ and an impregnation ratio（the mass ratio of PANOF to KOH） of 1：2 for an activation time of 1 b in 6 mol/L KOH solution exhibits a specific surface area of 3029 m^2/g, a mesoporosity of 84.2% and a specific capacitance of 288 F/g, and shows a good capacitive performance. The prepared ACF can be used as the electrode material for supercapacitors.     

基于玉米秸秆合成的多孔生物质炭材料及其电化学储能

以玉米秸秆为原料,合成了高比表面积(2167 m²/g)的多孔生物质炭材料。 优化实验条件即可获得性能最佳的生物质炭电极材料,其在电流密度为1 A/g时的比电容高达390 F/g。 更重要的是,以所得最佳多孔生物质炭为电极材料,3 mol/L 的KOH溶液为电解质,组装了液相对称超级电容器。 该超级电容器在功率密度为818 W/kg时,其能量密度高达7 Wh/kg,在循环10000圈后的电容保持率为91.1%。 同时,将两个这种超级电容器串联充电之后,能够点亮15个LED灯并驱动小风扇正常工作。 这些结果表明,将基于玉米秸秆的多孔生物质炭作为先进电极材料应用于超级电容器具有较大的实际应用价值。     

Peony pollen derived nitrogen-doped activated carbon for supercapacitor application

Peony pollen is a cheap and readily available biomass material with a relatively high protein content.In this work,it was employed as an N-rich precursor to prepare the nitrogen-doped porous carbon for supercapacitor application.The porous carbon microspheres were prepared through a hydrothermal method and subsequent carbonization process.Notably,ammonium borofruoride and potassium hydroxide were employed respectively as an etchant and an activator to modify the porosity of the materials.The as prepared ANPPCs-700 has a super high BET specific surface area of 824.69 m~2/g.The microstructure,chemical state and electrochemical properties of the product were investigated in detail.The prepared nitrogen-doped carbon microspheres exhibits excellent specific capacity of 209 F/g at a current density of lA/g and remained 92.5% of the initial capacitance after 5000 deep cycles at 5 A/g.     

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.     

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.     

Structure and Electrochemical Performance of Hollow Tube Activated Carbon Prepared from Cotton as Electrode Material for Electric Double Layer Capacitor

Hollow tube-like activated carbon(HTAC) was fabricated by a simple and efficient carbonization method with cotton as carbon precursor activated by KOH without any template. The activation time from 0 to 90 min showed no significant effect on the micro-morphology, but greatly influenced the specific surface area and electrochemical performance. In the end, it was found that the sample activated for 60 min(HTAC-60) has a higher specific surface area of 2600 m²/g, a larger pore volume of 1.52 cm³/g and a greater specific capacitance of 483 F/g at a current density of 0.2 A/g in 1 mol/L H₂SO₄. Moreover, the sample HTAC-60 shows excellent cycle stability(only 12.2% loss after 5000 cycles) and a high energy density of 67.1 or 37.2 W·h·kg^-1 at a power density of 200 or 1000 W/kg, respectively, operated in a voltage range of 0-1.0 V in 1 mol/L H₂SO₄. The results indicate that cotton can potentially be used as a raw material for producing low cost and high performance activated carbon electrode materials for electric double layer capacitor.     

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.     

电化学双电层电容器电极材料——豌豆荚基活性炭的制备与表征

以豌豆荚为碳源、ZnCl₂或KOH为活化剂制备了活性炭, 并用作双电层电容器的电极材料. 采用比表面及孔隙度分析仪表征了豌豆荚基活性炭的孔结构. 通过KOH或ZnCl₂活化后, 活性炭比表面积从1.69 m²·g^-1增大到2237或621 m²·g^-1. 采用循环伏安法和恒流充放电测试技术表征了豌豆荚基活性炭的电化学特性. 结果表明: 在6 mol·L^-1 KOH溶液中经KOH活化处理的活性炭的质量比电容高达297.5 F·g^-1, 并具有良好的充放电稳定性, 在5 A·g^-1的高电流密度下循环充放电500次后, 质量比电容仅衰减8.6%.     

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.     

Sulfur-doped CMK-5 with expanded lattice for high-performance lithium ion batteries

Heteroatom-doped porous carbon materials are very attractive for lithium ion batteries (LIBs) owing to their high specific surface areas, open pore structures, and abundant active sites. However, heteroatom-doped porous carbon with very high surface area and large pore volume are highly desirable but still remain a big challenge. Herein, we reported a sulfur-doped mesoporous carbon (CMK-5-S) with nanotubes array structure, ultrahigh specific surface area (1390 m²/g), large pore volume (1.8 cm³/g), bimodal pore size distribution (2.9 and 4.6 nm), and high sulfur content (2.5 at%). The CMK-5-S used as an anode material for LIBs displays high specific capacity, excellent rate capability and highly cycling stability. The initial reversible specific capacity at 0.1 A/g is as high as 1580 mAh/g and simultaneously up to 701 mAh/g at 1 A/g even after 500 cycles. Further analysis reveals that the excellent electrochemical storage performances is attributed to its unique structures as well as the expanded lattice by sulfur-doping.     

Novel Biomass-derived Hollow Carbons as Anode Materials for Lithium-ion Batteries

A novel hollow carbon derived from biomass lotus-root has been prepared by a one-step carbonization method. The carbon anode obtained at 900 ℃ showed the best electrochemical performance, corresponding to a high specific capacity of 445 mA∙h/g at 0.1 C, as well as excellent cycling stability after 500 cycles. Further investigation exhibits that the lithium storage of hollow carbon involves Li⁺ adsorption in the defect sites and Li⁺ insertion. The results showed that the intrinsic structure of lotus root can inspire us to prepare biomass carbon with a hollow structure as an excellent anode for lithium-ion batteries.     

静电纺氧化锰复合碳纳米纤维柔性膜的电化学性能

采用一步法静电纺丝技术制备了具有超亲水特性的氧化锰/碳纳米纤维(MnO_x/CNFs)复合柔性膜电极材料,并通过X射线衍射、扫描电子显微镜和透射电子显微镜等对复合材料进行了表征.电化学性能测试结果表明,复合材料的电容性能优于单一材料,醋酸锰质量分数为40%时制得的复合纳米纤维电极(MC-4)在1 A/g电流密度下,于2 mol/L KOH电解液中的比电容高达1112.5 F/g,10 A/g电流密度下循环3000次比容量保持在93.4%,具有很好的稳定性.MnO_x/CNFs复合材料电化学性能增强一方面是由于三维超亲水纤维膜结构有利于电解液的快速浸润渗透,从而极大缩短了传输到材料基质的有效路径;另一方面是由于碳和MnO_x的协同效应,包裹在MnO_x粒子周围的碳层避免了MnO_x在充放电过程中的体积膨胀效应,这2种叠加机制促进了电化学性能的提升.     

A hierarchical porous carbon membrane from polyacrylonitrile/polyvinylpyrrolidone blending membranes:Preparation,characterization and electrochemical capacitive performance

Novel hierarchical porous carbon membranes were fabricated through a simple carbonization procedure of well-defined blending polymer membrane precursors containing the source of carbon polyacrylonitrile （PAN） and an additive of polyvinylpyrrolidone （PVP）, which was prepared using phase inversion method. The as-fabricated materials were further used as the active electrode materials for supercapacitors. The effects of PVP concentration in the casting solution on structure feature and electrochemical capacitive performance of the as-prepared carbon membranes were also studied in detail. As the electrode material for supercapacitor, a high specific capacitance of 278.0 F/g could be attained at a current of 5 mA/cm2 and about 92.90% capacity retention could be maintained after 2000 charge/discharge cycles in 2 mol/L KOH solution with a PVP concentration of 0.3 wt% in the casting solution. The facile hierarchical pore structure preparation method and the good electrochemical capacitive performance make the prepared carbon membrane particularly promising for use in supercapacitor.     

蟹壳基氮/氧共掺杂多孔炭的原位制备及其超级电容器性能

采用废弃蟹壳为碳源,KOH为活化剂原位制备了氮/氧共掺杂多孔炭,并研究其作为电极材料在超级电容器中的应用。 固定蟹壳与KOH的质量比为5:3,考察了煅烧温度对所得炭材料产率、孔结构和氮氧含量的影响。 结果表明,蟹壳基炭材料的孔结构和氮/氧含量可通过改变煅烧温度调变。 随着煅烧温度从500 ℃上升至700 ℃,多孔炭的比表面积和孔体积逐渐增大,而氮/氧含量随温度升高则降低。 采用循环伏安和恒流充放电对所得材料的电化学性能进行测试。 结果表明,所得多孔炭的电化学性能取决于其孔结构与氮/氧表面性质的协同作用,其中煅烧温度为600 ℃所得的多孔炭比表面积为612 m²/g,氮和氧含量分别为3.53%和32.8%,在50 mA/g的电流密度下比电容达到310 F/g,循环1000次比电容仍然保持95%以上,展现出良好的电化学性能。     

Preparation and Supercapacitive Properties of Fe2O3/Active Carbon Nanocomposites

Fe₂O₃/active carbon(Fe₂O₃/AC) nanocomposites were readily fabricated by pyrolyzing Fe³⁺ impregnated active carbon in a nitrogen atmosphere. The as-prepared composites were studied by X-ray powder diffraction(XRD), X-ray photoelectron spectroscopy(XPS) and transmission electron microscopy(TEM). The capacitive property of the composites was investigated by cyclic voltammetry(CV) and galvanostatic charge-discharge test. Physical characterizations show that the γ-Fe₂O₃ fine grains dispersed in the AC well, with a mean size of 21.24 nm. Electrochemical tests in 6 mol/L KOH solutions indicate that the as-prepared nanocomposites exhibited improved capacitive properties. The specific capacitance(SC) of Fe₂O₃/AC nanocomposites was up to 188.4 F/g that was derived from both electrochemical double-layer capacitance and pseudo-capacitance, which was 78% larger than that of pristine AC. A symmetric capacitor with Fe₂O₃/AC nanocomposites as electrode showed an excellent cycling stability. The SC was only reduced by a factor of 9.2% after 2000 cycles at a current density of 1 A/g.     

Functionalized halloysite template-assisted polyaniline synthesis high-efficiency iron/nitrogen-doped carbon nanotubes towards nonprecious ORR catalysts

The iron-functionalized halloysite nanotudes is synthesized as a tubular template from an iron-nitrogen co-doped carbon nanocatalyst derived from the polyaniline pyrolysis of Oxygen reduction reaction (ORR). The use of iron-doped sites exposes the surface of the material to more graphite defects, effectively increasing the specific surface area of the carbon nanotubes and optimizing the density of the nitrogen-containing active sites. We have found that this iron-nitrogen co-doped carbon nanotube exhibits a superior ORR performance with a half-wave potential of 0.77 V in the 0.1 mol L⁻¹ KOH aqueous solution. The electrochemical stability test was carried out at 1600 rpm. The half-wave potential showed only a degradation of 8 mV, which was better than the commercial 20% Pt/C (18 mV). This study developed an economical method for the direct synthesis of iron-nitrogen co-doped carbon nanotubes using a hard template.