Paraffin-based shape-stable phase change materials with graphene/carbon nanotube three-dimensional network structure

A novel kind of paraffin-based shape-stable phase change materials (SSPCMs) was prepared by introducing paraffin into reduced graphene oxide (rGO)/carbon nanotubes (CNTs) aerogel via vacuum-assisted impregnation method. The effects of ratio of rGO to CNTs in 3D network structure on morphology, structure and property of paraffin-based SSPCMs were investigated. The rGO/CNTs 3D network structure with high thermal conductivity, served as thermally conductive skeleton together. In particular, CNTs was used as a secondary heat conductive filler, which could be well dispered in the SSPCMs to conduct heat synergistically. The SSPCMs exhibited high thermal conductivity and excellent shape-stability. And the thermal conductivity of SSPCMs can be regulated by adjusting the ratio of rGO to CNTs in aerogels. These results indicate that 3D rGO/CNTs aerogels have advantages as thermally conductive skeleton, and can endow phase transition materials with stable shape, so as to realize the application of phase change materials in the field of heat dissipation.     

温和条件可控制备三维还原氧化石墨烯凝胶及其性能

为了实现石墨烯类三维气凝胶在温和环境条件下的大面积可控制备和高性能化,本文应用水合肼作为还原剂,通过低温预冷冻结合室温自然干燥,实现了室温还原自组装法可控制备直径30 cm的大面积三维还原氧化石墨烯(3D-RGO)气凝胶。该方法制备条件温和,不需任何加热条件和特殊冷冻干燥设备。通过对气凝胶制备过程中还原时间、预冷冻时间、预冷冻温度和反应容器进行控制,可以有效调节气凝胶的形状、表面浸润性、体积收缩率等,实现3D-RGO气凝胶的可控制备。该气凝胶不会出现明显的体积收缩和结构破裂,为具有约500μm的稳定孔径和3.8 mg/cm³的低密度的蜂窝状结构,并能够从90%的压缩应变下快速地恢复到初始状态,其干燥过程体积收缩率<5%;同时该石墨烯气凝胶展现良好稳定的导电性,在压缩应变从0%增加到90%时,其导电率从17.3 S/m增加至115.2 S/m。这种方法经济高效且易于制备出大面积的3D-RGO。     

耐高温氧化铝气凝胶隔热复合材料研究进展

氧化铝气凝胶是一种高孔隙率、低密度、高比表面积、耐高温和低热导的纳米多孔材料, 在高温隔热领域(如航天飞行器热防护系统、工业窑炉保温材料等)具有广阔的应用前景。但是, 纯氧化铝气凝胶因耐温性(1000 ℃以上)、力学性能和高温隔热性能相对较差难以直接应用, 需要引入增强相和遮光组分制备成气凝胶复合材料以进行改善。本文对耐高温氧化铝气凝胶的制备、氧化铝气凝胶隔热复合材料的制备及性能等方面的最新研究进展进行了综述。研究人员通过原位掺杂改性、沉积改性、有机链和炭涂层改性等方法提高了氧化铝气凝胶的热稳定性。在氧化铝气凝胶中引入晶须、颗粒、多孔骨架和纤维等增强相, 能够大幅提高其力学性能; 纤维和遮光剂的协同作用, 能够提高氧化铝气凝胶抑制红外辐射的能力, 显著降低高温热导率。本文还提出了后续的研究方向：对氧化铝气凝胶的密度、微观结构进行精细调控, 再引入合适的异质元素和遮光剂,以进一步提高气凝胶的热稳定性和复合材料的隔热性能;深入研究复合材料在高温下结构和性能的演化, 以及氧化铝气凝胶和增强相之间的相互作用。作为一种新型的隔热材料, 氧化铝气凝胶复合材料将在高温隔热领域发挥其优势并逐步实现广泛应用。     

Robust and Stable Cu Nanowire@Graphene Core–Shell Aerogels for Ultraeffective Electromagnetic Interference Shielding

Cu nanowires (CuNWs) are considered as a promising candidate to develop high performance metal aerogels, yet the construction of robust and stable 3D porous structures remains challenging which severely limits their practical applications. Here, graphene‐hybridized CuNW (CuNW@G) core–shell aerogels are fabricated by introducing a conformal polymeric coating and in situ transforming it into multilayered graphene seamlessly wrapped around individual CuNWs through a mild thermal annealing process. The existence of the outer graphene shell reinforces the 3D bulk structure and significantly slows down the oxidation process of CuNWs, resulting in improved mechanical property and highly stable electrical conductivity. When applied in electromagnetic interference shielding, the CuNW@G core–shell aerogels exhibit an average effectiveness of ≈52.5 dB over a wide range (from 8.2 to 18 GHz) with negligible degradation under ambient conditions for 40 d. Mechanism analysis reveals that the graphene shell with functional groups enables dual reflections on the core–shell and a multiple dielectric relaxation process, leading to enhanced dielectric loss and energy dissipation within the core–shell aerogels. The flexible core–shell‐structured CuNW@G aerogels, with superior mechanical robustness and electrical stability, have potential applications in many areas such as advanced energy devices and functional composites.     

基于纳米材料的气凝胶制备及应用

气凝胶是一种三维多孔材料,具有孔隙率高、比表面积大、密度低等特性。以纳米材料构筑气凝胶可进一步调控孔隙结构、改善机械强度,同时还能赋予气凝胶高导电性、低热导率、高吸附性和隔音吸声等特性,在储能、保温隔热、吸附材料等领域有重要的应用。重点对近年以纳米颗粒、纳米纤维素、碳纳米纤维、碳纳米管、石墨烯等不同形态纳米材料构筑的气凝胶的制备、结构、性能和应用进行了综述,同时展望了气凝胶的发展前景与方向。     

Paraffin/carbon aerogel phase change materials with high enthalpy and thermal conductivity

Two kinds of carbon aerogels, graphene aerogels (GA) and carbon nanotubes-graphene aerogels (CGA), were prepared by modified hydrothermal method. The form-stable phase change materials (PCMs) were fabricated by adsorbing paraffin into carbon aerogels. Morphology, structure, form stability and thermal property were characterized by scanning electron microscope (SEM), in situ X-ray diffraction (in situ XRD) and differential scanning calorimeter (DSC). The results showed that GA presented wrinkled surface textures with curling edges, and carbon nanotubes (CNTs) were interspersed or attached to GA sheets. The phase transition temperature and the phase change enthalpy of the GA/paraffin PCM composite were 48.7 °C and 223.2 J/g, respectively. Thermal and mechanical properties of PCM composites achieved a qualitative leap with the adding of carbon aerogels. The PCM composites had a thermal conductivity of about 2.182 W/m K at the carbon aerogels loading fraction of 2 wt%. The form-stable PCM composites with high thermal conductivity and high enthalpy could be promising for thermal energy storage applications in construction field.     

Conductive,self-cleaning,and short-circuit proof multi-functional graphene aerogel composite fibers

This work reports the superior properties of flexible multi-functional composite fibers based on graphene aerogel fibers. With the addition of phase change materials, the graphene aerogel fibers were synthesized by wet spinning and supercritical drying. The phase change materials can improve the structural uniformity and thermal stability of the composite fibers. The fibers coated with polydimethylsiloxane and fluorocarbon can respond to various external stimuli (e.g., electrons, photons, and heat), as well as have excellent properties of shape compliance, self-cleaning, and insulated surfaces. After coating fluorocarbon, the maximum water contact angle of graphene aerogel fibers increases from 132.18° to 151.77°. It is worth mentioning that adding an insulation layer of polydimethylsiloxane avoids the high-temperature problem caused by the short circuit of graphene aerogel fibers. The short-circuit temperature of graphene aerogel fibers is as high as 65 °C, while that of the composite fiber is only 41.5 °C after coating with polydimethylsiloxane. The temperature of graphene aerogel fibers with polyethylene glycol can increase to 39.3 °C under simulated sunlight. In addition, graphene aerogel fibers have excellent electrical conductivity (4.85?×?10³ S m^?1) at 300 K. After coating with polyethylene glycol, its electrical conductivity is still as high as 2.95?×?10³ S m^?1. The good electrical conductivity makes the aerogel fibers have promising application in advanced wearable systems.

     

Conductive resilient graphene aerogel via magnesiothermic reduction of graphene oxide assemblies

Graphene aerogels are desirable for energy storage and conversion, as catalysis supports, and as adsorbents for environmental remediation. To produce graphene aerogels with low density, while maintaining high electrical conductivity and strong mechanic performance, we synthesized graphene aerogels by the magnesiothermic reduction of a freeze-dried graphene oxide (GO) self-assembly and subsequent etching of the formed MgO in acid solution. The reduced graphene oxide (rGO) aerogel samples exhibited densities as low as 1.1 mg·cm^?3. The rGO aerogel was very resilient, exhibiting full recoveryeven after being compressed by strains of up to 80%; its elastic modulus (E) scaled with density (ρ) as E～ρ². The rGO aerogels also exhibited high conductivities (e.g., 27.7 S·m^?1 at 3.6 mg·cm^?3) and outperformed many rGO aerogels fabricated by other reduction processes. Such outstanding properties were ascribed to the microstructures inherited from the freeze-dried GO self-assembly and the magnesiothermic reduction process.

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SiOC气凝胶/柔性陶瓷纤维复合材料的制备和性能

选用正硅酸乙酯(TEOS)和甲基三甲氧基硅烷(MTMS)为前驱体,用溶胶-凝胶法制备不同C/Si(原子比,下同)比的SiOC气凝胶,再用大气喷涂法将其喷涂在柔性陶瓷纤维隔热毡中制备出SiOC气凝胶/柔性陶瓷纤维复合材料。C/Si比,是影响SiOC气凝胶/柔性陶瓷纤维复合材料性能的主要因素。随着C/Si比的提高SiOC溶液的凝胶时间延长且更易浸入隔热毡,材料的密度和热导率先降低后提高。C/Si比为0.67的材料热导率最低,其室温热导率为0.026 W/m·K,1000℃时的热导率为0.174 W/m·K。与未改性的隔热毡相比,其热导率显著降低,尤其是在高温下热导率降低47%;同时,这种材料还具有优异的耐高温和抗氧化性能,在1200℃空气中静烧1 h后试样的质量损失只约为1%,静烧3 h后约为5%,随着C/Si比的提高其质量损失随之提高;同时,SiOC气凝胶复合材料还具有良好的疏水性能、柔性和回弹性。     

Graphene coating makes carbon nanotube aerogels superelastic and resistant to fatigue

Lightweight materials that are both highly compressible and resilient under large cyclic strains can be used in a variety of applications. Carbon nanotubes offer a combination of elasticity, mechanical resilience and low density, and these properties have been exploited in nanotube-based foams and aerogels. However, all nanotube-based foams and aerogels developed so far undergo structural collapse or significant plastic deformation with a reduction in compressive strength when they are subjected to cyclic strain. Here, we show that an inelastic aerogel made of single-walled carbon nanotubes can be transformed into a superelastic material by coating it with between one and five layers of graphene nanoplates. The graphene-coated aerogel exhibits no change in mechanical properties after more than 1?×?10(6) compressive cycles, and its original shape can be recovered quickly after compression release. Moreover, the coating does not affect the structural integrity of the nanotubes or the compressibility and porosity of the nanotube network. The coating also increases Young's modulus and energy storage modulus by a factor of ～6, and the loss modulus by a factor of ～3. We attribute the superelasticity and complete fatigue resistance to the graphene coating strengthening the existing crosslinking points or 'nodes' in the aerogel.     

碳纳米纤维增强聚酰亚胺复合气凝胶的合成与性能EI北大核心CSCD

以4,4′-二氨基二苯醚(ODA)、均苯四甲酸二酐(PMDA)为单体,酸化碳纳米纤维(a-CNF)为增强材料,采用溶胶-凝胶方式成型,运用冷冻干燥技术制备PI复合气凝胶。对复合气凝胶的形貌、隔热、吸波以及压缩性能等进行表征分析。研究结果表明:随着a-CNF含量的增加,PI复合气凝胶的收缩率从45.52%降至35.32%,密度也随之从0.084 g/cm^(3)降至0.069 g/cm^(3),气凝胶孔洞分布呈增大增宽趋势。a-CNF的引入有效抑制了PI复合气凝胶的收缩率,热导率降低;整个体系的导电损耗增加,同时由于气凝胶的多孔结构提供了较好的阻抗匹配,使得PI复合气凝胶的反射损耗(RL)在8.3 GHz达到-9.7 dB。加入质量分数为15%的CNF/PI复合气凝胶压缩强度和压缩模量分别是纯PI气凝胶的近1.5倍和2倍。     

纤维素纳米纤丝-还原氧化石墨烯/聚苯胺气凝胶柔性电极复合材料的制备与性能

利用高长径比的纤维素纳米纤丝（CNF）与片层结构的氧化石墨烯（GO）形成的CNF-GO复合水凝胶经抗坏血酸还原制备出CNF-还原氧化石墨烯（rGO）复合水凝胶材料。通过冷冻干燥法得到CNF-rGO复合气凝胶,并进一步通过苯胺单体在CNF-rGO复合气凝胶的孔道内原位聚合制备出CNF-rGO/聚苯胺（PANI）气凝胶柔性电极复合材料。研究了不同苯胺、CNF和GO的质量比对CNF-rGO/PANI气凝胶柔性电极复合材料的结构形貌和电化学性能的影响。结果表明,苯胺原位聚合后所得CNF-rGO/PANI复合气凝胶仍具有紧密的三维多孔网络结构。与rGO/PANI气凝胶电极复合材料相比,CNF-rGO/PANI气凝胶电极复合材料具有更理想的电容行为。当CNF与GO质量比为60∶40,PANI添加量为0.1 mol时,CNF-rGO/PANI气凝胶电极复合材料比电容可达85.9 Fg-1,且其电化学性能几乎不受弯曲程度的影响,展现出了良好的柔韧性和电化学性能。      

Al2O3-SiO2复合气凝胶的制备及改性剂对其结构与隔热性能的影响

以AlCl₃·6H₂O为前驱体,采用离子交换工艺和溶胶-凝胶法,在正硅酸四乙酯（TEOS）乙醇溶液中浸泡实现Al₂O₃和SiO₂的复合,经表面改性和常温常压干燥制备出低成本、无杂质离子、低热导率的Al₂O₃-SiO₂复合气凝胶。探索了不同有机硅烷改性剂对Al₂O₃-SiO₂复合气凝胶结构和隔热性能的影响。结果表明,在改性剂为三甲氧基甲基硅烷（MTMS）,改性环境为中性（pH为7）时,Al₂O₃-SiO₂复合气凝胶表现出最均匀的微观结构,SiO₂和Al₂O₃主要以无定形形式存在。MTMS可有效减少Al₂O₃-SiO₂湿凝胶表面的-OH基团,形成Si-O-Si和Al-O-Si基团。Al₂O₃-SiO₂气凝胶比表面积和孔体积分别达到574 m2/g和2.3 cm3/g,热导率低至0.029 W（m·K）-1。以上研究为促进气凝胶材料在隔热领域的应用提供了支持。      

Polyimide aerogels cross-linked through amine functionalized polyoligomeric silsesquioxane

We report the first synthesis of polyimide aerogels cross-linked through a polyhedral oligomeric silsesquioxane, octa(aminophenyl)silsesquioxane (OAPS). Gels formed from polyamic acid solutions of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), bisaniline-p-xylidene (BAX) and OAPS were chemically imidized and dried using supercritical CO(2) extraction to give aerogels having density around 0.1 g/cm(3). The aerogels are greater than 90 % porous, have high surface areas (230 to 280 m(2)/g) and low thermal conductivity (14 mW/m-K at room temperature). Notably, the polyimide aerogels cross-linked with OAPS have higher modulus than polymer reinforced silica aerogels of similar density and can be fabricated as both monoliths and thin films. Thin films of the aerogel are flexible and foldable making them an ideal insulation for space suits, and inflatable structures for habitats or decelerators for planetary re-entry, as well as more down to earth applications.     

轻质高效保温材料掺杂硅气凝胶

利用正硅酸甲脂（ＴＭＯＳ）为原料的溶胶－凝胶过程，摸索了不同反应条件下形成凝胶的规律，并选用ＴｉＯ２粉末及玻璃纤维作为掺杂剂，采用超临界干燥处理制备出掺ＴｉＯ２的硅气凝胶，通过对红外光谱以及不同温度和气压条件下热导率的测量，讨论了不同成份配比以及相应的热传输过程对材料热导率的影响。结果表明，密度为２６０ｋｇ／ｍ＾３的掺杂硅气凝胶在８００Ｋ时的热导率为０．０３８ｗ／ｍ．ｋ，是一种新型的轻质高效保温材     

氮化硼气凝胶的制备及其应用进展

氮化硼气凝胶是一类以固体为骨架、气体为分散介质的, 具有三维多孔网络结构的新型纳米材料, 展现出高比表面积、高孔隙率、低密度等优异的性能。此外, 相比于石墨烯气凝胶, 氮化硼气凝胶拥有更好的绝缘性、抗氧化性、热稳定性和化学稳定性, 因此它在气体吸附、催化、污水净化、导热/隔热等领域极具应用前景。本文结合国内外研究现状, 重点介绍了硬模板法、软模板法、低维氮化硼组装法和无模板法制备氮化硼气凝胶的结构和性能特点, 总结了其在关键领域的重要应用, 并对其未来发展方向进行了展望。     

Elastic Aerogels of Cellulose Nanofibers@Metal–Organic Frameworks for Thermal Insulation and Fire Retardancy

Metal–organic frameworks(MOFs)with high microporosity and relatively high thermal stability are potential thermal insulation and flame-retardant materials.However,the difficulties in processing and shaping MOFs have largely hampered their applications in these areas.This study outlines the fabrication of hybrid CNF@MOF aerogels by a stepwise assembly approach involving the coating and cross-linking of cellulose nanofibers(CNFs)with continuous nanolayers of MOFs.The cross-linking gives the aerogels high mechanical strength but superelasticity(80%maximum recoverable strain,high specific compression modulus of^200 MPa cm3 g−1,and specific stress of^100 MPa cm3 g−1).The resultant lightweight aerogels have a cellular network structure and hierarchical porosity,which render the aerogels with relatively low thermal conductivity of^40 mW m−1 K−1.The hydrophobic,thermally stable MOF nanolayers wrapped around the CNFs result in good moisture resistance and fire retardancy.This study demonstrates that MOFs can be used as efficient thermal insulation and flame-retardant materials.It presents a pathway for the design of thermally insulating,superelastic fire-retardant nanocomposites based on MOFs and nanocellulose.     

基于数字图像相关方法的气凝胶复合材料各向异性热变形测量

在热防护材料及结构高温力学性能研究中,测量其在热载荷与机械载荷作用下产生的变形是重要且基础的工作。基于数字图像相关方法,建立了可实现800℃变形测量的非接触式测量系统。针对陶瓷纤维增强SiO_2气凝胶复合材料,从面外和面内两个材料方向,以25℃为参考温度,试验测量了材料加热至300~800℃范围内不同温度时产生的热变形。研究结果表明,在此试验系统基础上的变形测量方法可用来测量此类热防护材料的高温变形。陶瓷纤维增强SiO2气凝胶复合材料的高温热变形具有明显的各向异性,面外方向上表现为"收缩",面内方向上表现为"膨胀"。SiO_2气凝胶基体中的颗粒团聚以及增强纤维在面内方向上的铺层分布是导致热变形各向异性的主要原因。     

石墨烯/炭气凝胶的制备及其结构与性能研究

以间苯二酚(R)和甲醛(F)为炭前驱体原料, 通过溶胶-凝胶法制备石墨烯/炭气凝胶复合材料。采用XRD、Raman、SEM和N₂吸附/脱附等对样品进行结构表征。结果表明: 石墨烯为R和F的聚合提供形核场所, R和F首先在氧化石墨烯(GO)表面聚合, 随着RF含量的增加, 复合炭气凝胶(RF)结构从石墨烯薄片层为骨架的三维网络, 经RF基炭球包裹于石墨烯的网络结构, 最终转变为球形团簇交联的三维网络。石墨烯/炭气凝胶复合材料的比表面积随着RF的增加先增大后减小。当GO与RF质量比为1︰100时, GO/RF-100用作超级电容器电极材料, 在6 mol/L KOH电解液中的比电容达169 F/g, 具有较好的电容特性。     

Ultralight Multifunctional Carbon‐Based Aerogels by Combining Graphene Oxide and Bacterial Cellulose

Nanostructured carbon aerogels with outstanding physicochemical properties have exhibited great application potentials in widespread fields and therefore attracted extensive attentions recently. It is still a challenge so far to develop flexible and economical routes to fabricate high‐performance nanocarbon aerogels, preferably based on renewable resources. Here, ultralight and multifunctional reduced graphene oxide/carbon nanofiber (RGO/CNF) aerogels are fabricated from graphene oxide and low‐cost, industrially produced bacterial cellulose by a three‐step process of freeze‐casting, freeze‐drying, and pyrolysis. The prepared RGO/CNF aerogel possesses a very low apparent density in the range of 0.7–10.2 mg cm^?3 and a high porosity up to 99%, as well as a mechanically robust and electrically conductive 3D network structure, which makes it to be an excellent candidate as absorber for oil clean‐up and an ideal platform for constructing flexible and stretchable conductors.