Preparation of controlled porosity carbon aerogels for energy storage in rechargeable lithium oxygen batteries

Porous carbon aerogels are prepared by polycondensation of resorcinol and formaldehyde catalyzed by sodium carbonate followed by carbonization of the resultant aerogels in an inert atmosphere. Pore structure of carbon aerogels is adjusted by changing the molar ratio of resorcinol to catalyst during gel preparation and also pyrolysis under Ar and activation under CO₂ atmosphere at different temperatures. The prepared carbons are used as active materials in fabrication of composite carbon electrodes. The electrochemical performance of the electrodes has been tested in a Li/O₂ cell. Through the galvanostatic charge/discharge measurements, it is found that the cell performance (i.e. discharge capacity and discharge voltage) depends on the morphology of carbon and a combined effect of pore volume, pore size and surface area of carbon affects the storage capacity. A Li/O₂ cell using the carbon with the largest pore volume (2.195 cm³/g) and a wide pore size (14.23 nm) showed a specific capacity of 1290 mA h g⁻¹.     

Waste cotton Fabric/MXene composite aerogel with heat generation and insulation for efficient electromagnetic interference shielding

Electromagnetic interference (EMI) shielding materials have become more and more indispensable due to serious electromagnetic-radiation pollution. Herein, waste cotton cellulose aerogels were prepared by dissolving waste cotton fabrics (WCF) in NaOH/urea aqueous solution, and MXene nanosheets were subsequently deposited on the cellulose aerogels by a facile dip coating method to obtain WCF/MXene composite aerogels. The WCF/MXene composite aerogels with highly porous network structure show remarkable electrical conductivity (8.2 Ω/sq of surface resistance), high EMI shielding effectiveness (EMI SE) in the range of 2–18 GHz (39.3–48.1 dB). The WCF/MXene aerogel possesses high SSE and SSE/t of 677.94–829.74 dB cm³ g^?1 and 3512.62–4299.17 dB cm² g^?1, respectively (2–18 GHz). In addition, the heating temperature of WCF/MXene composite aerogels reaches 199 °C when 3 V positive voltage is applied on them. The WCF/MXene composite aerogels possess excellent electromagnetic shielding effectiveness, heat generation property and insulation, which can be potentially used as multifunctional materials for EMI shielding, electrical-heating and high temperature protection.     

SiBCN ceramic aerogel/graphene composites prepared via sol-gel infiltration process and polymer-derived ceramics (PDCs) route

The SiBCN ceramic aerogel/graphene composites were synthesized by combining a simple sol-gel infiltration process with CO₂ supercritical drying technology and polymer-derived ceramics route. In order to select the best preceramic sample for sintering, the micromorphology of PSNB aerogel/graphene composites fabricated with different graphene oxide solution concentrations were investigated. The microstructure evolution of the prepared SiBCN ceramic aerogel/graphene composites and phase composition were studied by SEM, TEM and XRD, the pore structure of the preceramic composites pyrolyzed at 1200 °C was tested by specific surface area and pore size analyzer. Furthermore, the compressive strain-stress curve and toughening mechanisms of composites were also investigated in detail. The results showed that all the preceramic composites and obtained ceramic aerogel composites possessed the mesoporous structure. The basic structure of SiBCN aerogel network changed from the initial spherical particles accumulation to the nanowires lapping with the sintering temperature increased from 800 °C to 1200 °C. After pyrolyzing at 1200 °C, the specific surface area and pore volume for the sample were 101.61 m² g⁻¹ and 1.43 cm³ g⁻¹, respectively, and a small amount of β-SiC crystalline phases were formed in amorphous ceramic matrix and had an relatively uniform distribution. Moreover, the paepared ceramic aerogel composites possessed a certain degree of toughness, the toughening mechanisms of composite samples mainly included the crack deflection, graphene pull-out, graphene bridging and graphene crumpling.     

Hierarchically Fe-doped porous carbon derived from phenolic resin for high performance supercapacitor

Supercapacitors are promising for high power application in the recent years. In particular, the conversion of simple and available carbon materials into economic and high performance electrical devices receives excellent scientific and technological interest. This paper reports a one-step strategy for synthesizing hierarchical porous carbon derived from phenolic resin (PR), which is then used to configure electric double-layer capacitors (EDLCs). Here, a carbon material with a flexible porous structure, large specific surface area, and high graphitization degree is prepared using potassium ferrate (K₂FeO₄) to catalytically activate PR and to realize synchronous carbonization and graphitization. This method overcomes the disadvantage of time-consuming, high-cost, and environmentally unfriendly. In addition, the as-prepared carbon material has a high specific surface area (1086 m² g^?1) and a large pore size (3.07 nm), which can increase the transfer rate of electrolyte ions. The specific capacitance of the obtained electrode material is 315 F g^?1 at 1.0 A g^?1, and the optimized electrode material has an ultra-long cycle lifetime (capacitance retention rate is 96.3% after 10,000 cycles). Thus, the hierarchically Fe-doped porous carbon material derived from PR material is expected to realize high rate capacitance for supercapacitor applications.     

Starch-derived carbon aerogels with high-performance for sorption of cationic dyes

Environmentally green carbon aerogels have been prepared as adsorbents for dye-containing wastewater. The aerogels were prepared by carbonization of starch aerogels synthesized from soluble starch through a sol-gel process followed by drying at ambient pressure. The Brunauer-Emmett-Teller (BET) surface areas and pore size distribution were measured by N₂ adsorption/desorption, and the surface zeta-potential and microstructure of carbon aerogels were characterized using a scanning electron microscope (SEM) and zeta-potential analyzer. SEM images indicate that the carbon aerogels consist of flakes with side length of 60-120 μm and thickness of 3-4 μm. The flakes are irregular in shape and composed of spherical carbon nanoparticles of 10-30 nm. The carbon aerogels have both microporous and mesoporous structures and exhibit high specific surface areas, the highest value is 1571 m²/g. The mean diameter of the micropores is 0.89 nm and that of the mesopores is 2-10 nm. At pH = 10, the carbon aerogels have a zeta-potential of −40 mV and exhibit high adsorption capacities for cationic dyes, such as crystal violet (CV), methyl violet (MV) and methylene blue (MB), from aqueous solution. The largest adsorption capacities for CV, MV and MB are 1515, 1423 and 1181 mg/g, respectively.     

Ultralight,high-surface-area,multifunctional graphene-based aerogels from self-assembly of graphene oxide and resol

The self-assembly between graphene oxide sheets and resol-type phenolic prepolymers was investigated as a method to form three-dimensional porous carbon objects with high surface areas and low densities. After freeze-drying and subsequent pyrolysis of the assembled hydrogels, ultralight graphene/carbon composite aerogels with high surface areas and porosity, good conductivity, and well-defined bulk shape were obtained. By adjusting the amount of graphene oxide and resol in the precursor mixture, aerogels with a density as low as 3.2 mg/cm³ or a surface area as high as 1019 m²/g could be prepared. It is proposed that resol molecules are first adsorbed on the surface of graphene oxide sheets, and then the surface-coated sheets are crosslinked by the polymerization of resol prepolymers. The absorption performance was evaluated for the aerogel with the lowest density. Due to the high porosity, the aerogel displayed fast absorption rates for organic solvents as well as high absorption efficiencies. The high conductivity of the aerogels permits good performance as binderless monolithic electrodes for supercapacitors.     

A machinable carbon aerogel composite with a low thermal conductivity and enhanced mechanical properties

ABSTRACT

Carbon aerogels are prepared via the sol–gel polymerisation of resorcinol with formaldehyde, followed by supercritical drying and carbonisation. The fabricated carbon aerogels have low densities in the range 0.028–0.196?g?cm^?3, ultra-low thermal conductivities in the range 0.0259–0.0707?W?(m?K)^?1 and high specific surface areas (>520?m²?g^?1). The carbon aerogel composites are reinforced with short carbon fibres by adding the carbon fibres to the resorcinol–formaldehyde solution to reduce their brittle nature and improve their machinability. The compressive strength of the composites containing 2?wt-% carbon fibres is 1.75?MPa, which is 56% higher than that of pure carbon aerogel. Both fracture toughness and compressive strength of these composites are improved. These composites also have good machinability, with the ability to maintain their shape after being machined with traditional steel tools. Furthermore, the composites with nanoporous structure exhibit ultra-low thermal conductivity up to 1400°C.     

Large size and low density SiOC aerogel monolith prepared from triethoxyvinylsilane/tetraethoxysilane

Crack-free silicon oxycarbide (SiOC) aerogel monolith was fabricated by pyrolysis of precursor aerogel prepared from triethoxyvinylsilane/tetraethoxysilane (VTES/TEOS) using sol-gel process and ambient drying. Effects of different precursors, the amount of base catalyst (NH₄OH) and the heating rate during pyrolysis on the properties such as monolithicity, bulk density, surface area and pore size distribution of aerogels were investigated. The results show that the crack-free SiOC aerogel can be easily obtained from VTES/TEOS as compared to that of methyltriethoxysilanes/tetraethoxysilane (MTES/TEOS) and phenyltriethoxysilanes/tetraethoxysilane (PhTES/TEOS) precursors. The influence of heating rate during pyrolysis process on shrinkage rate, ceramic yield and surface area of the SiOC aerogels could be ignored, while the variation in the amount of NH₄OH exerted a strong impact on the properties of SiOC aerogels. Increasing the amount of NH₄OH resulted in the decrease of bulk density and surface area of SiOC aerogels from 0.335 g/cm³ and 488 m²/g to 0.265 g/cm³ and 365 m²/g. The resultant SiOC aerogels exhibit high compressive strength (1.45–3.17 MPa). ²⁹Si MAS NMR spectra revealed the retention of Si-C bond in the SiOC aerogels after pyrolysis at 1000 °C. The present work demonstrates VTES/TEOS is a promising co-precursors to easily and low cost synthesize large size SiOC aerogel monolith.     

Preparation and characterization of porous,biomorphic SiC ceramic with hybrid pore structure

Bio-carbon template (charcoal) was prepared by carbonizing pine wood at 1200 °C under vacuum, and was impregnated with phenolic resin/SiO₂ sol mixture by vacuum/pressure processing. Porous SiC ceramics with hybrid pore structure, a combination of tubular pores and network SiC struts in the tubular pores, were fabricated via sol–gel conversion, carbonization and carbothermal reduction reaction at elevated temperatures in Ar atmosphere. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscope (SEM) were employed to characterize the phase identification and microstructural changes during the C/SiO₂ composites-to-porous SiC ceramic conversion. Experimental results show that the density of C/SiO₂ composite increases with the number of impregnation procedure, and increases from 0.32 g cm⁻³ of pine-derived charcoal to 1.5 g cm⁻³ of C/SiO₂ composite after the sixth impregnation. The conversion degree of charcoal to porous SiC ceramic increases as reaction time is lengthened. The resulting SiC ceramic consists of β-SiC with a small amount of α-SiC. The conversion from pine charcoal to porous SiC ceramic with hybrid pore structure improves bending strength from 16.4 to 42.2 MPa, and decreases porosity from 76.1% to 48.3%.     

Sucrose derived microporous–mesoporous carbon for advanced lithium–sulfur batteries

A microporous–mesoporous carbon has been successfully prepared via carbonization of sucrose followed by heat treatment process. The obtained porous carbon possesses abundant micropores and mesopores, which can effectively increase the sulfur loading. The composite exhibited a remarkable initial capacity of 1185 mAh g^?1 at 0.2 A g^?1 and maintained at 488 mAh g^?1 after 200 cycles, when employed for lithium?sulfur batteries. Moreover, the composite displayed enhanced rate capabilities of 1124, 914 and 572 mAh g^?1 at 0.2, 0.5 and 1.0 A g^?1. The outstanding electrochemical capabilities and facile low?cost preparation make the new microporous–mesoporous carbon as an excellent candidate for lithium sulfur batteries.     

Surface Modification of Silica Aerogels Dried with 2-Methyl-1-Propanol in the Sub-Critical Pressure

Silica aerogels were made by sol-gel techniques using industrial silicon derivatives (polyethoxydisiloxanes, E-40), followed by drying under sub-critical pressure with iso-butanol. The shrinkage (linear), specific surface area, S_BET, SEM, TEM and the pore size distribution of the silica aerogels were investigated. The results show that the shrinkage (linear) is below 5%, diameter of the silica particles is about 6 nm and the pore size of the silica aerogels is 10 nm. The specific surface area of the silica aerogel is 559.2 m²/g. IR and NMR techniques were used to determine the organic groups on the silica matrix, GC/MS was also introduced to analyse the composition of the recycled iso-butanol. The surface modification and the reactions of iso-butanol to the silica aerogel are also discussed.     

In-situ synthesis and textural evolution of the novel carbonaceous SiC/mullite aerogel via polymer-derived ceramics route

A novel carbonaceous SiC/mullite composite aerogel is derived from catechol-formaldehyde/silica/alumina hybrid aerogel (CF/SiO₂/AlOOH) via polymer-derived ceramics route (PDCR). The effects of the reactants concentrations on the physicochemical properties of the carbonaceous SiO₂/Al₂O₃ aerogel and SiC/mullite aerogel are investigated. The mechanism of the textural and structural evolution for the novel carbonaceous SiC/mullite is further discussed based on the experimental results. Smaller reactants concentration is favorable to formation of mullite. Reactants concentration of 25% is selected as the optimal condition in considering of the mullite formation and bulk densities of the preceramic aerogels. Spherical large silica particles are also produced during heat treatment, and amorphous silica is remained after this reaction. With further heat treatment at 1400 °C, silicon carbide and mullite coexist in the aerogel matrix. The mullite addition decreases the temperature of SiC formation, when compared with the conventional methods. However, after heat treatment at 1450 °C, the amount of mullite begins to decrease due to the further reaction between carbon and mullite, forming more silicon carbide and alumina. The carbonaceous SiC/mullite can be transferred to SiC/mullite binary aerogel after carbon combustion under air atmosphere. The carbonaceous SiC/mullite has a composition of SiC (31%), mullite (19.1%), SiO₂ (14.4%), and carbon (35%). It also possesses a 6.531 nm average pore diameter, high surface area (69.61 m²/g), and BJH desorption pore volume (0.1744 cm³/g). The oxidation resistance of the carbonaceous SiC/mullite is improved for 85 °C when compared with the carbon based aerogel.     

Monolithic chitosan-silica composite aerogel with comprehensive performances prepared by SBG-FD method

Silica aerogels are viewed as potential thermal insulation materials because they are highly porous, adiabatic and lightweight. The lack of mechanical strength and hygroscopicity are the main barriers to their application. In order to tackle these issues, a direct sol-blending-gel combing freezing drying (SBG-FD) technique is used to create trimethylchlorosilane (TMCS)-modified natural polysaccharide-reinforced chitosan-silica aerogel (CS-T-SA) in this work. This brand-new CS-T-SA possesses three-dimensional network structure, and its thermal conductivity reaches 0.0360 W m⁻¹ k⁻¹ at 30 °C with bulk density as low as 0.0485 g cm⁻³ and volume shrinkage to a minimum of 5%. Hydrophobic modification with TMCS gives the composite aerogel a promisingly high hydrophobicity with the water contact angle of 135.1°. In comparison to conventional silica aerogels, the chitosan-silica aerogels exhibit improved mechanical characteristics, with no brittle rupture up to at least 80% strain and stress at 80% strain values of 0.285–0.486 MPa. Remarkably, aerogel monoliths can be machined and sculpted using tools. This demonstration to produce monolithic and machinable, mesoporous aerogels with low-density from bio-sourced, renewable and nontoxic precursors, combined with good thermal stability and hydrophobicity opens up new possibilities for biopolymer-silica aerogel applications and represents a significant approach toward the commercialization of biopolymer-silica aerogels.     

Fiber Reinforced Polyimide Aerogel Composites with High Mechanical Strength for High Temperature Insulation

Glass fiber/polyimide aerogel composites are prepared by adding glass fiber mat to a polyimide sol derived from diamine, 4,4′‐oxydianiline, p‐phenylene diamine, and dianhydride, 3,3′,4,4′‐biphenyltetracarboxylic dianhydride. The fiber felt acts as a skeleton for support and shaping, reduces aerogel shrinkage during the preparation process, and improves the mechanical strength and thermal stability of the composite materials. These composites possess a mesoporous structure with densities as low as 0.143–0.177 g cm^?3, with the glass fiber functioning to improve the overall mechanical properties of the polyimide aerogel, which results in its Young's modulus increasing from 42.7 to 113.5 MPa. These composites are found to retain their structure after heating at 500 °C, in contrast to pure aerogels which decompose into shrunken ball‐like structures. These composites maintain their thermal stability in air and N₂ atmospheres, exhibiting a low thermal conductivity range of 0.023 to 0.029 W m^?1 K^?1 at room temperature and 0.057to 0.082 W m^?1 K^?1 at 500 °C. The high mechanical strengths, excellent thermal stabilities, and low thermal conductivities of these aerogel composites should ensure that they are potentially useful materials for insulation applications at high temperature.     

Rapid preparation of Palygorskite/Al2O3 composite aerogels with superhydrophobicity,high-temperature thermal insulation and improved mechanical properties

Al₂O₃ aerogels are widely employed in heat insulation and flame retardancy because of their unique combination of low thermal conductivity and exceptional high-temperature stability. However, the mechanical properties of Al₂O₃ aerogel are poor, and the preparation time is considerably long. In this study, we present a simple and scalable approach to construct monolithic Pal/Al₂O₃ composite aerogels using solvothermal treatment instead of traditional solvent replacement, which remarkably shortened the preparation time. Subsequently, to obtain stable superhydrophobicity (θ > 152°), the Pal/Al₂O₃ aerogel was modified by gas-phase modification method. The obtained Pal/Al₂O₃ composite aerogels demonstrate the integrated properties of low density (0.078–0.106 g/cm³), low thermal conductivity (1000 °C, 0.143 W/(m·K)), good mechanical properties (Young's modulus, 1.6 MPa), and good heat resistance. The monolithic Pal/Al₂O₃ composite aerogels with improved mechanical performance and improved thermal stability can show great potential in the field of thermal insulation.     

酚醛基炭气凝胶的研究进展

炭气凝胶是一种多孔纳米炭材料,具有低密度、高孔隙率、高比表面积、优异的导电性和良好的成型性能等优点,是炭材料研究的热点和重要方向。本文旨在通过阐明酚醛基炭气凝胶的制备原料和制备工艺的发展过程,从而突出未来酚醛基炭气凝胶的发展方向。基于此,本文首先重点介绍了酚醛基炭气凝胶的制备方法,主要包括溶胶-凝胶化、干燥以及炭化过程三个最主要的步骤;进而详述了以三种不同的前体,即间苯二酚、苯酚、生物质单宁/木质素分别制备酚醛基炭气凝胶的方法及其优缺点;接下来对酚醛基炭气凝胶作为吸附材料（气体吸附/液体吸附）的吸附量以及在电化学储能以及其他领域的应用进行了综述;最后对酚醛基炭气凝胶未来的研究方向和发展前景进行了总结和展望。文章指出,传统的以间苯二酚为原料辅以超临界干燥的方法制备的酚醛基炭气凝胶,原料成本较高,反应条件苛刻,实际生产应用受限;以苯酚取代间苯二酚,亦或是采用冷冻干燥等方法改进其制备工艺,可以大幅度降低原料和生产成本;但未来的发展方向和重点将是绿色、可再生的生物质原料（单宁、木质素、腰果酚等）及复合气凝胶材料的研发。因此,酚醛基炭气凝胶在未来的发展还需要进一步改进其制备工艺和方法,拓宽其原料来源,从而提高性能,扩大应用领域。     

Electrospun porous carbon nanofibers/TiO2 composite coated over carbon cloth- A flexible electrode for capacitive deionization

The combination of porous carbon matrix and metal oxide is trending for capacitive deionization (CDI) due to their synergistic electrochemical behaviour and properties. In this research, a flexible electrode based on electrospun porous carbon nanofibers and TiO₂ nanoparticles (particle size ～7 nm) i.e., PCNFs/TiO₂ composite coated over carbon cloth is developed. A facile in-situ activation procedure using sacrificial polymer is adopted over typical chemical activation treatment to synthesize PCNFs/TiO₂ composite. PCNFs/TiO₂ composite is prepared in two steps, possessing a high specific surface area of ～343 m² g^?1 and pore volume of 0.038 cm³ g^?1. Interestingly, CDI unit assembled with PCNFs/TiO₂ composite based flexible electrodes delivers the large salt electrosorption capacity of 204.8 mg g^?1 at voltage 1.2 V in a salt solution of concentration 500 ppm and conductivity 880 μS cm^?1. The excellent adsorption capacity retention of 96.4% up to ten adsorption-regeneration cycles can be a tempting option for future flexible CDI applications.     

Zirconia aerogels: Effect of acid used in the sol-gel process on morphological properties

Zirconia aerogels have been prepared from butanolic zirconium(IV) tetra-n-butoxide diluted in ethanol via stoichiometric hydrolysis with water in ethanol. Nitric acid or acetic acid were used to modify the sol-gel process. After calcination in air at 573 K, the aerogel prepared with nitric acid possesses a specific surface area of 240 m² · g^–1 and a unimodal pore size distribution with a maximum at ca. 24 nm, whereas the use of acetic acid results in an aerogel with specific surface area of 228 m² · g^–1 and bimodal pore size distribution with maxima at 3 and 65 nm. The crystalline fractions of both aerogels are predominantly tetragonal with a small contribution of monoclinic ZrO₂.     

New carbon materials with high porosity in the 1-7 nm range obtained by chemical activation with phosphoric acid of resorcinol-formaldehyde aerogels

Chemical activation of resorcinol-formaldehyde aerogels with phosphoric acid results in materials containing both intra-particle microporosity (pore volume ∼0.18 cm³g⁻¹ and mean-pore-width ∼1 nm) and inter-particle micro/mesoporosity. The latter forms as a result of partial collapse of the mesopore structure of the organic aerogel and can be controlled by varying the phosphoric acid/organic aerogel ratio. Increasing this ratio leads to higher pore volume and size and it was possible to obtain micro/mesopore volumes as high as 1.23 cm³g⁻¹ with pore widths up to ∼7 nm. Over 90% of these pores were accessible even after blocking all of the ultramicroporosity by pre-adsorption of n-nonane.     

High surface area methyltriethoxysilane-derived aerogels by ambient pressure drying

In this paper we report the synthesis of methyltriethoxysilane (MTES) based aerogels by non-supercritical/ambient pressure drying. The alcogels have been aged in different concentrations of silane precursor solutions before drying and aerogels with low density and high porosity were obtained. The 60% vol silane aged aerogel shows a surface area of 416 m²/g with a pore volume of 0.99 cm³/g and a maximum surface area of 727 m²/g was obtained for 80% vol silane aged aerogel. The non-silane aged sample possess a surface area of 471 m²/g with a total pore volume of 0.83 cm³/g. The aerogels show broad pore-size distribution. The FT-IR studies reveal the retention of Si–C bond in the network and the formation of a hydrophobic gel. The ²⁹Si magic angle spinning nuclear magnetic resonance (²⁹Si MAS-NMR) studies were also employed to characterize the local environment around the silicon atoms and to obtain information on the condensation degree of the gel network. By varying the hydrolysis pH, highly flexible aerogels have also been successfully prepared. The porosity studies on the flexible aerogels are also presented here.