Recent Advances in Hollow Porous Carbon Materials for Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries are considered as one of the most potential next‐generation rechargeable batteries due to their high theoretical energy density. However, some critical issues, such as low capacity, poor cycling stability, and safety concerns, must be solved before Li–S batteries can be used practically. During the past decade, tremendous efforts have been devoted to the design and synthesis of electrode materials. Benefiting from their tunable structural parameters, hollow porous carbon materials (HPCM) remarkably enhance the performances of both sulfur cathodes and lithium anodes, promoting the development of high‐performance Li–S batteries. Here, together with the templated synthesis of HPCM, recent progresses of Li–S batteries based on HPCM are reviewed. Several important issues in Li–S batteries, including sulfur loading, polysulfide entrapping, and Li metal protection, are discussed, followed by a summary on recent research on HPCM‐based sulfur cathodes, modified separators, and lithium anodes. After the discussion on emerging technical obstacles toward high‐energy Li–S batteries, prospects for the future directions of HPCM research in the field of Li–S batteries are also proposed.     

基于纤维素纤维的多孔碳材料的制备及应用

采用选择性表面溶解（SSD）法将纤维素纤维表面部分溶解,固化后形成多孔结构,最后在Ar气氛中炭化制得多孔碳（HPC-SSD）材料,HPC-SSD材料具有大的比表面积和三维多孔结构。通过SEM、BET、FTIR、XRD及电化学测试,系统地研究了针对纤维素纤维的两种活化预处理方法对HPC-SSD材料的形貌、化学组成、比表面积及电化学性能的影响。通过与纤维素纤维直接炭化所得的多孔碳（HPC）材料的相关性能进行比较发现,HPC-SSD材料的成孔过程更加稳定,有利于大量微孔的形成。采用去离子水→丙酮→二甲基乙酰胺对纤维素纤维进行活化预处理,制得的HPC-SSD材料比电容为226 F·g-1（两电极体系）,是HPC材料的4.5倍,比未经过活化预处理的HPC-SSD材料提高了40%。      

Hierarchical porous carbon obtained from directly carbonizing carex meyeriana for high-performance supercapacitors

Hierarchical porous carbon materials with high surface area are facilely prepared by directly carbonizing carex meyeriana without any extra activation procedure. The as-prepared porous carbon samples possess high Brunauer–Emmett–Teller (BET) surface areas (in the?~?518–742 m² g^?1 range) and unique hierarchical porous structure containing macropore channels and mesopores and micropores developed in the wall of macropores. These intriguing characteristics make the as-prepared hierarchical porous carbon samples a promising electrode material for supercapacitors. The capacitive performance was measured in the three-electrode system with 6 M KOH electrolyte. The hierarchical porous carbon prepared at the carbonization temperature of 1000 °C presents a high specific capacitance of 178.6 F g^?1 at a current density of 0.5 A g^?1, a good rate performance ( about 65.2% retention ratio at the current density of 20 A g^?1), and an excellent cycling stability (no obvious performance fading after 10,000 cycles). In addition, the fabricated two-electrode device achieves an energy density of 4.33 Wh kg^?1 at a high power density of 5 kW kg^?1. These results provide a green and facile method to synthesize the electrode material from biomass for high-performance supercapacitors.

     

A facile preparation of pomegranate-like porous carbon by carbonization and activation of phenolic resin prepared via hydrothermal synthesis in KOH solution for high performance supercapacitor electrodes

High electrochemical performance pomegranate-like porous carbon was synthesized by the carbonization and activation of phenolic resin which was prepared by adding phenolic resin monomer mixture into KOH aqueous solution and hydrothermal treatment. In the process of hydrothermal, KOH solution could hinder the polymerization of phenolic resin monomer to form big phenolic resin particles. During the carbonization, phenolic resin plays the role of forming small particles and binder during carbonization, which can simultaneously achieve high specific surface area and form three dimensional structures to improve the conductivity. The results showed that pomegranate-like porous carbon composed of small nanometer-scale particles was observed. The obtained porous carbon electrode materials had a high content of micropores with specific surface area as high as 2199.9 m² g⁻¹. The porous carbon exhibited a high specific capacitance of 341.3 F g⁻¹ at 0.1 A g⁻¹, good rate capability with 71.0% retention from 0.1 to 5 A g⁻¹. Moreover, it showed high capacitance retention of 96.1% after 5000 cycles at a scan rate of 50 mV s⁻¹, indicating excellent cycling stability. The assembled symmetrical supercapacitor showed high energy densities of 17.0 Wh kg⁻¹ and 8.5 Wh kg⁻¹ with the corresponding power densities of 49.6 W kg⁻¹ and 1.8 kW kg⁻¹, respectively. The facile method could be a promising candidate for preparing porous carbon electrode materials with excellent electrochemical performance in the fields of supercapacitors.     

Nitrogen Codoped Unique Carbon with 0.4 nm Ultra‐Micropores for Ultrahigh Areal Capacitance Supercapacitors

A full understanding of ion transport in porous carbon electrodes is essential for achieving effective energy storage in their applications as electrochemical supercapacitors. It is generally accepted that pores in the size range below 0.5 nm are inaccessible to electrolyte ions and lower the capacitance of carbon materials. Here, nitrogen‐doped carbon with ultra‐micropores smaller than 0.4 nm with a narrow size distribution, which represents the first example of electrode materials made entirely from ultra‐microporous carbon, is prepared. An in situ electrochemical quartz crystal microbalance technique to study the effects of the ultra‐micropores on charge storage in supercapacitors is used. It is found that ultra‐micropores smaller than 0.4 nm are accessible to small electrolyte ions, and the area capacitance of obtained sample reaches the ultrahigh value of 330 µF cm^?2, significantly higher than that of previously reported carbon‐based materials. The findings provide a better understanding of the correlation between ultra‐micropore structure and capacitance and open new avenues for design and development of carbon materials for the next generation of high energy density supercapacitors.     

基于海藻酸钠交联的NiO/C复合材料制备及其储锂性能

NiO作为过渡金属氧化物代表,具有能量密度较高、成本低的优点,在锂离子电池负极材料的应用中引起了广泛关注。通过海藻酸钠与金属离子的自主交联反应,以及碳化、氧化过程,制备了低成本的多孔纳米NiO/C复合材料。得到的复合材料中,NiO纳米颗粒分散均匀且被石墨化碳层包覆,并嵌入多孔相互连通的碳基体中,在提升复合材料整体导电性的同时抑制了活性材料在电化学反应中的体积膨胀。将其用作锂离子电池负极材料时,NiO/C复合材料在0.1,1 A/g的电流密度下分别具有608.2,307.2 mAh/g的比容量,并且在0.1 A/g电流密度下经过100圈循环后仍保持448 mAh/g的比容量,显示出优良的循环稳定性。优良的电化学性能充分显示出NiO/C复合材料在锂离子电池负极材料中的应用潜能。     

The control of porosity at nano scale in resorcinol formaldehyde carbon aerogels

Organic aerogels were synthesized by sol–gel polymerization of resorcinol (R) with formaldehyde (F) catalyzed by sodium carbonate (C) followed by vacuum drying. The influence of the resorcinol/sodium carbonate ratio (R/C) on the porous structure of the resultant aerogels was investigated. The nitrogen adsorption–desorption measurements show that the aerogels possess a well developed porous structure and mesoporosity was found to increase with increasing the R/C ratio. Carbon aerogels were obtained by carbonization of RF aerogels. The carbonization temperature impacts the microstructure of the aerogels by pore transformations during carbonization probably due to the formation of micropores and shrinkage of the gel structure. The results showed that a temperature of 1073 K is more effective in the development of the pore structure of the gel. Activated carbon aerogels were obtained from the CO₂ activation of carbon aerogels. Activation results in an increase in the number of both micropores and mesopores, indicative of pore creation in the structure of the carbon. Activation at higher temperatures results in a higher degree of burn off and increases the pore volume and the surface area remarkably without change of the basic porous structure, pore size, and pore size distribution.     

Encapsulation of MnS Nanocrystals into N,S-Co-doped Carbon as Anode Material for Full Cell Sodium-Ion Capacitors

Sodium-ion capacitors(SICs)have received increasing interest for grid stationary energy storage application due to their affordability,high power,and energy densities.The major challenge for SICs is to overcome the kinetics imbalance between faradaic anode and nonfaradaic cathode.To boost the Na+reaction kinetics,the present work demonstrated a high-rate MnS-based anode by embedding the MnS nanocrystals into the N,S-co-doped carbon matrix(MnS@NSC).Benefiting from the fast pseudocapacitive Na+storage behavior,the resulting composite exhibits extraordinary rate capability(205.6 mAh g−1 at 10 A g−1)and outstanding cycling stability without notable degradation after 2000 cycles.A prototype SIC was demonstrated using MnS@NSC anode and N-doped porous carbon(NC)cathode;the obtained hybrid SIC device can display a high energy density of 139.8 Wh kg−1 and high power density of 11,500 W kg−1,as well as excellent cyclability with 84.5%capacitance retention after 3000 cycles.The superior electrochemical performance is contributed to downsizing of MnS and encapsulation of conductive N,S-co-doped carbon matrix,which not only promote the Na+and electrons transport,but also buffer the volume variations and maintain the structure integrity during Na+insertion/extraction,enabling its comparable fast reaction kinetics and cyclability with NC cathode.     

Compressing Carbon Nanocages by Capillarity for Optimizing Porous Structures toward Ultrahigh‐Volumetric‐Performance Supercapacitors

High volumetric energy density combined with high power density is highly desired for electrical double‐layer capacitors. Usually the volumetric performance is improved by compressing carbon material to increase density but at the much expense of power density due to the deviation of the compressed porous structure from the ideal one. Herein the authors report an efficient approach to increase the density and optimize the porous structure by collapsing the carbon nanocages via capillarity. Three samples with decreasing sizes of meso‐ and macropores provide us an ideal model system to demonstrate the correlation of volumetric performance with porous structure. The results indicate that reducing the surplus macropores and, more importantly, the surplus mesopores is an efficient strategy to enhance the volumetric energy density while keeping the high power density. The optimized sample achieves a record‐high stack volumetric energy density of 73 Wh L^?1 in ionic liquid with superb power density and cycling stability.     

Condiment‐Derived 3D Architecture Porous Carbon for Electrochemical Supercapacitors

The one‐step synthesis of porous carbon nanoflakes possessing a 3D texture is achieved by cooking (carbonization) a mixture containing two condiments, sodium glutamate (SG) and sodium chloride, which are commonly used in kitchens. The prepared 3D porous carbons are composed of interconnected carbon nanoflakes and possess instinct heteroatom doping such as nitrogen and oxygen, which furnishes the electrochemical activity. The combination of micropores and mesopores with 3D configurations facilitates persistent and fast ion transport and shorten diffusion pathways for high‐performance supercapacitor applications. Sodium glutamate carbonized at 800 °C exhibits high charge storage capacity with a specific capacitance of 320 F g^?1 in 6 m KOH at a current density of 1 A g^?1 and good stability over 10 000 cycles.     

染料敏化太阳电池多级孔炭对电极的制备及性能研究

以F127为模板剂, 采用自组装与后活化相结合制备了具有微孔-介孔结构的多级孔炭. N2吸附等温线分析表明后活化可在介孔炭孔壁上生成大量微孔. 电化学阻抗谱测量表明多级孔炭电极对I₃^-还原反应的催化活性明显高于介孔炭电极, 电荷迁跃电阻为0.3 Ω·cm². 多级孔炭电极催化活性高是由于它具有较高的比表面和特殊的多级孔结构, 有效比表面积较高. 以多级孔炭电极为对电极组装染料敏化太阳电池, 电池的短路电流密度、开路电压和填充因子分别为0.624V、15.44 mA/cm²和0.67, 相应的光电转换效率为6.48%, 比介孔炭对电极电池的光电转换效率提高了11.5%.     

Hierarchical Porous SWCNT Stringed Carbon Polyhedrons and PSS Threaded MOF Bilayer Membrane for Efficient Solar Vapor Generation

Interfacial solar vapor generation is considered to be an efficient and eco‐friendly technology for harvesting solar energy and providing freshwater. However, the efficient and long‐term steady evaporation of seawater under 1 sun becomes a critical issue when it comes to practical applications. Based on this issue, a special double‐layer structure, which contains a metal–organic‐framework‐derived hierarchical porous carbon membrane (HPCM) for solar absorption and a polystyrene sulfonate (PSS)@Cu₃(BTC)₃?3H₂O (HKUST‐1)/single‐walled carbon nanotube (SWCNT) (PHS) membrane for water supply and salt blocking, is designed in this work. The converted heat is utilized efficiently in situ to drive the evaporation of water‐trapped HPCM. The PHS membrane with PSS modified channels successfully prevents the deposition of salt. Due to the synergistic combination of the HPCM and PHS membranes, the device exhibits a remarkably high water evaporation rate of 1.38 kg m^?2 h^?1 and solar‐vapor generation efficiency of 90.8% under 1 sun.     

Nitrogen and oxygen co-doped mesoporous carbon spheres as capacitive anode for high performance sodium-ion capacitors

The poor rate capability of battery-type anode is usually the bottleneck of the power-energy outputs of a hybrid alkaline metal ion capacitor.In this work,nitrogen and oxygen co-doped mesoporous carbon spheres with excellent rate performance and cycle stability are used as anode materials of sodium ion capacitors(SICs).The high N and O element doping levels as well as the amorphous and mesoporous structure have enabled prominent capacitive Na ion storage behavior,which in turn match well with the capacitive cathode in the hybrid device.Under optimum conditions,the SIC delivers a high energy density of 103.1 Wh kg-1 at a power density of 205.6 W kg-1.Even at a high power density of 7520 W kg-1,an energy density of 23.5 Wh kg-1 is still maintained.Moreover,a robust cycle stability with capacity retention of 84.6％after 2500 cycles at 1 A g-1 is maintained.Such excellent electrochemical performances convincingly demonstrate that the all-carbon based SICs with the highly capacitive N and O co-doped mesoporous carbon anode can be promising Na ion-based energy storage devices alternative to their Li ion-based counterparts.     

Scalable 2D Hierarchical Porous Carbon Nanosheets for Flexible Supercapacitors with Ultrahigh Energy Density

2D carbon nanomaterials such as graphene and its derivatives, have gained tremendous research interests in energy storage because of their high capacitance and chemical stability. However, scalable synthesis of ultrathin carbon nanosheets with well‐defined pore architectures remains a great challenge. Herein, the first synthesis of 2D hierarchical porous carbon nanosheets (2D‐HPCs) with rich nitrogen dopants is reported, which is prepared with high scalability through a rapid polymerization of a nitrogen‐containing thermoset and a subsequent one‐step pyrolysis and activation into 2D porous nanosheets. 2D‐HPCs, which are typically 1.5 nm thick and 1–3 µm wide, show a high surface area (2406 m² g^?1) and with hierarchical micro‐, meso‐, and macropores. This 2D and hierarchical porous structure leads to robust flexibility and good energy‐storage capability, being 139 Wh kg^?1 for a symmetric supercapacitor. Flexible supercapacitor devices fabricated by these 2D‐HPCs also present an ultrahigh volumetric energy density of 8.4 mWh cm^?3 at a power density of 24.9 mW cm^?3, which is retained at 80% even when the power density is increased by 20‐fold. The devices show very high electrochemical life (96% retention after 10000 charge/discharge cycles) and excellent mechanical flexibility.     

Three-dimensional carbon nanotube-textile anode for high-performance microbial fuel cells

Microbial fuel cells (MFCs) harness the metabolism of microorganisms, converting chemical energy into electrical energy. Anode performance is an important factor limiting the power density of MFCs for practical application. Improving the anode design is thus important for enhancing the MFC performance, but only a little development has been reported. Here, we describe a biocompatible, highly conductive, two-scale porous anode fabricated from a carbon nanotube-textile (CNT-textile) composite for high-performance MFCs. The macroscale porous structure of the intertwined CNT-textile fibers creates an open 3D space for efficient substrate transport and internal colonization by a diverse microflora, resulting in a 10-fold-larger anolyte-biofilm-anode interfacial area than the projective surface area of the CNT-textile. The conformally coated microscale porous CNT layer displays strong interaction with the microbial biofilm, facilitating electron transfer from exoelectrogens to the CNT-textile anode. An MFC equipped with a CNT-textile anode has a 10-fold-lower charge-transfer resistance and achieves considerably better performance than one equipped with a traditional carbon cloth anode: the maximum current density is 157% higher, the maximum power density is 68% higher, and the energy recovery is 141% greater.     

Synthesis of nanostructured fibers consisting of carbon coated Mn3O4 nanoparticles and their application in electrochemical capacitors

Nanostructured composite fibers consisting of carbon coated Mn3O4 nanoparticles (Mn3O4@C) were prepared from thermal decomposition of manganese alginate fibers produced by wet-spinning technique, and investigated with SEM, TEM, XRD, nitrogen adsorption-desorption isotherms, and electrochemical tests toward energy storage. It is found that the as-obtained Mn304@C fibers consist of plenty of nano-sized Mn3O4 crystals with even diameter of 10-15 nm and carbon coating layer with a thickness of 1-2 nm. The composite fibers exhibit also a porous structure consisting of both micropores and mesopores. The electrochemical performances of Mn3O4@C fibers were examined by cyclic voltammetry and galvanostatic charge-discharge techniques. The results indicate that Mn3O4@C fibers possess a higher specific capacitance and superior rate capability when used as electrode materials for supercapacitor compared with commercial Mn3O@4. The improved performances of Mn3O4C fibers can be attributed to the nano-dimension of Mn3O4 particles, the thin carbon coating layer and the nanopores existing among Mn304@C nanoparticles.     

Boosting Zn‐Ion Energy Storage Capability of Hierarchically Porous Carbon by Promoting Chemical Adsorption

The construction of advanced Zn‐ion hybrid supercapacitors (ZHSCs) with high energy density is promising but still challenging, especially at high current densities. In this work, a high‐energy and ultrastable aqueous ZHSC is demonstrated by introducing N dopants into a hierarchically porous carbon cathode for the purpose of enhancing its chemical adsorption of Zn ions. Experimental results and theoretical simulations reveal that N doping not only significantly facilitates the chemical adsorption process of Zn ions, but also greatly increases its conductivity, surface wettability, and active sites. Consequently, the as‐fabricated aqueous ZHSC based on this N‐doped porous carbon cathode displays an exceptionally high energy density of 107.3 Wh kg^?1 at a high current density of 4.2 A g^?1, a superb power density of 24.9 kW kg^?1, and an ultralong‐term lifespan (99.7% retention after 20 000 cycles), substantially superior to state‐of‐the‐art ZHSCs. Particularly, such a cathode also leads to a quasi‐solid‐state device with satisfactory energy storage performance, delivering a remarkable energy density of 91.8 Wh kg^?1. The boosted energy storage strategy by tuning the chemical adsorption capability is also applicable to other carbon materials.     

基于四羟甲基甘脲前驱体的新型含氮富微孔活性炭制备及其性能研究

以四羟甲基甘脲为碳前驱体,采用KOH活化法处理得到双电层电容器用多孔活性炭材料。考察了不同碳化、活化温度对活性炭比电容的影响。结果表明,在850℃碳化,650℃活化处理时其电容性能最好,SEM和比表面与孔径分布测试说明TA-850-650表面富集微孔;恒流充放电与循环伏安测试结果表明TA-850-650的比电容在电流密度为0.2A/g时可达527F/g。     

Porous carbons prepared from deoiled asphalt and their electrochemical properties for supercapacitors

Porous carbon was prepared from deoiled asphalt by conventional NaOH activation process and by the combination of nano-sized MgO template method and NaOH activation process. The electrochemical properties used as supercapacitors electrode material were evaluated in 7 M KOH aqueous solution. Porous carbon sample obtained by NaOH activation possessed more micropores and higher specific surface area, resulting in a higher specific capacitance of 235 F g^− 1 at low charge-discharge current of 50 mA g^− 1. For the combination method, the resultant carbons possessed higher capacitance and good capacitance maintaining at high current, with a capacitance of nearly twice as that of the former at current density of 10 A g^− 1, due to their abundant mesopores.     

Porous carbons

Carbon in dense as well as porous solid form is used in a variety of applications. Activated porous carbons are made through pyrolysis and activation of carbonaceous natural as well as synthetic precursors. Pyrolysed woods replicate the structure of original wood but as such possess very low surface areas and poor adsorption capacities. On activation, these exhibit increased adsorption volumes of 0.5-0.8 cm³/gm and surface areas of 700–1800 m²/gm depending on activation conditions, whether physical or chemical. Former carbons possess mixed pore size distribution while chemically activated carbons predominantly possess micropores. Thus, these carbons can be used for adsorption of wide distributions of molecules from gas to liquid. The molecular adsorption within the pores is due to single layer or multilayer molecule deposition at the pore walls and hence results in different types of adsorption isotherm. On the other hand, activated carbon fibres with controlled microporous structure and surface area in the range of 2500 m²/gm can be developed by controlled pyrolysis and physical activation of amorphous carbon fibres. Active carbon fibres with unmatchable pore structure and surface characteristics are present and futuristic porous materials for a number of applications from pollution control to energy storage.