Enhanced Potassium‑Ion Storage of the 3D Carbon Superstructure by Manipulating the Nitrogen‑Doped Species and Morphology

Potassium-ion batteries(PIBs)are attractive for gridscale energy storage due to the abundant potassium resource and high energy density.The key to achieving high-performance and large-scale energy storage technology lies in seeking eco-efficient synthetic processes to the design of suitable anode materials.Herein,a spherical sponge-like carbon superstructure(NCS)assembled by 2D nanosheets is rationally and efficiently designed for K+storage.The optimized NCS electrode exhibits an outstanding rate capability,high reversible specific capacity(250 mAh g^(−1) at 200 mA g^(−1) after 300 cycles),and promising cycling performance(205 mAh g^(−1) at 1000 mA g^(−1) after 2000 cycles).The superior performance can be attributed to the unique robust spherical structure and 3D electrical transfer network together with nitrogen-rich nanosheets.Moreover,the regulation of the nitrogen doping types and morphology of NCS-5 is also discussed in detail based on the experiments results and density functional theory calculations.This strategy for manipulating the structure and properties of 3D materials is expected to meet the grand challenges for advanced carbon materials as high-performance PIB anodes in practical applications.

3D Carbon Frameworks for Ultrafast Charge/Discharge Rate Supercapacitors with High Energy‑Power Density

Carbon-based electric double layer capacitors(EDLCs)hold tremendous potentials due to their high-power performance and excellent cycle stability.However,the practical use of EDLCs is limited by the low energy density in aqueous electrolyte and sluggish diffusion kinetics in organic or/and ionic liquids electrolyte.Herein,3D carbon frameworks(3DCFs)constructed by interconnected nanocages(10-20 nm)with an ultrathin wall of ca.2 nm have been fabricated,which possess high specific surface area,hierarchical porosity and good conductive network.After deoxidization,the deoxidized 3DCF(3DCFDO)exhibits a record low IR drop of 0.064 V at 100 A g^−1 and ultrafast charge/discharge rate up to 10 V s^−1.The related device can be charged up to 77.4%of its maximum capacitance in 0.65 s at 100 A g^−1 in 6 M KOH.It has been found that the 3DCF-DO has a great affinity to EMIMBF4,resulting in a high specific capacitance of 174 F g^−1 at 1 A g^−1,and a high energy density of 34 Wh kg^−1 at an ultrahigh power density of 150 kW kg^−1 at 4 V after a fast charge in 1.11 s.This work provides a facile fabrication of novel 3D carbon frameworks for supercapacitors with ultrafast charge/discharge rate and high energy-power density.

Biomass-Derived Nitrogen and Sulfur Co-Doped 3D Carbon Networks with Interconnected Meso-Microporous Structure for High-Performance Supercapacitors

Three-dimensional(3D)carbon networks have been explored as promising capacitive materials thanks to their unique structural features such as large ion-accessible surface area and interconnected porous networks,thus enhancing both ions and electrons transport.Here,sustainable bacterial cellulose(BC)is used both precursor and template for facile synthesis of free-standing N,S-codoped 3Dcarbon networks(a-NSC)by the pyrolysis and activation of polyrhodanine coated BC.The synthesized a-NSC shows highly conductive interconnected porous networks(24S·cm^(-1)),large surface area(1 420m^2·g^(-1))with hierarchical meso-microporosity,and high-level heteroatoms codoping(N:3.1%in atom,S:3.2%in atom).Benefitting from these,a-NSC as binder-free electrode exhibits an ultrahigh specific capacitance of 340F·g^(-1)(24μF·cm^(-2))at the current density of 0.5A·g^(-1)in 6MKOH electrolyte,high-rate capability(71%at 20A·g^(-1))and excellent cycle stability.Furthermore,the assembled symmetrical supercapacitor displays a much short time constant of 0.35sin 1MTEABF4/AN electrolyte,obtaining a maximum energy density of 32.1W·h·kg^(-1 )at power density of 637W·kg^(-1).The in situ multi-heteroatoms doping enables biocellulose-derived carbon networks to exploit its full potentials in energy storage applications,which can be extended to other dimensional carbon nanostructures.

N/S co-doped 3D carbon framework prepared by a facile morphology-controlled solid-state pyrolysis method for oxygen reduction reaction in both acidic and alkaline media

Developing high-performance non-precious metal electrocatalysts for oxygen reduction reaction(ORR)is crucial for the commercialization of fuel cells and metal-air batteries.However,doped carbon-based materials only show good ORR activity in alkaline medium,and become less effective in acidic environment.We believe that an appropriate combination of both ionic and electronic transport path,and well dopant distribution of doped carbon-based materials would help to realize high ORR performance un-der both acidic and alkaline cond让ions.Accordingly,a nitrogen and sulfur co-doped carbon framework with hierarchical through-hole structure is fabricated by morphology-controlled solid-state pyrolysis of poly(aniline-co-2-ami no thiophenol)foam.The uniform high concentrations of nitrogen and sulfur,high intrinsic conductivity,and integrated three dimensional ionic and electronic transfer passageways of the 3D porous structure lead to synergistic effects in catalyzing ORR.As a result,the limiting current density of the carbonized poly(aniline-co-2-aminothiophenol)foam is equivalent to commercial Pt/C in acidic environment,and twice the latter in alkaline medium.

基于裂缝闭合理论和3D打印的导流能力预测方法

酸蚀裂缝导流能力对于酸压方案的优化和产能评估具有十分重要的意义,但是在酸蚀导流能力测试过程中存在高闭合压力下岩心柱破裂情况,影响实验数据的准确性。基于以上问题,综合采用3D扫描和3D打印技术以及受压情况下裂缝闭合理论对酸蚀裂缝导流能力进行研究。首先对岩样进行酸蚀实验,通过逆向建模技术获取到酸蚀后岩心三维模型,采用SLA3D打印技术制备含粗糙壁面的三维岩心模型,对酸蚀岩心和3D打印岩心开展不同围压下渗流实验。运用离散化数据处理方法,结合赫兹接触模型和N-K模型编写导流能力预测界面,使用数值模拟方法反映闭合应力下裂缝形变情况。研究结果表明,结合真实岩体三维数字模型及SLA3D打印技术制备真实岩样,为制作复杂裂缝岩心模型提供了有效途径;酸蚀岩心和3D打印岩心导流能力实验结果、3D打印岩心实验结果和数值模拟结果误差均小于7.7%,数值模拟与碳酸盐岩心实验值的误差小于9.6%;以低闭合压力下实验和模拟结果为基础可以预测高闭合压力下裂缝导流能力,提出的研究方法为定量化表征酸蚀裂缝导流能力提供了可靠途径。

3D打印混凝土抗碳化性能各向异性及成因分析

受挤出式工艺的影响,3D打印混凝土中存在较多的界面,影响着打印混凝土的耐久性能。为了探明3D打印成型混凝土抗碳化性能的各向异性变化规律,通过碳化试验研究了三种水胶比3D打印混凝土沿X、Y、Z三个方向的碳化行为。基于压汞试验和X-CT扫描获取了3D打印混凝土的孔隙特征和分布规律,从微观层面阐释3D打印混凝土抗碳化性能的变化机理。结果表明:孔隙与3D打印混凝土的碳化行为有着密切联系,层条间界面因条带堆叠产生了更多孔隙,因而CO_(2)在界面位置扩散速度更快,碳化深度更大;受界面的影响,打印混凝土的抗碳化性能具有明显的各向异性;基体部位材料的抗碳化性能优于层间界面,层间界面的抗碳化性能优于条间界面;水灰比越低,材料抗碳化性能越好;当CO_(2)在混凝土中扩散时,受层条间大孔隙的影响,打印成型混凝土中形成了未碳化岛。

玻璃与碳纤维混杂增强复合材料3D打印与实验

本研究基于热塑性材料熔融沉积成型工艺,研制了双喷头连续玻璃纤维与碳纤维混杂增强热塑性复合材料结构增材制造平台,制备了不同混杂比的纤维增强热塑性复合材料结构试件,分析了不同结构试件的弯曲力学性能与失效模式,探索了嵌入碳纤维智能层的混杂纤维增强热塑性复合材料的力阻行为。结果表明:比较纯热塑性材料结构件,玻璃纤维增强复合材料结构件弯曲强度提高了115.99%,碳纤维增强复合材料结构件弯曲强度提高了198.76%;玻璃纤维与碳纤维混杂增强复合材料结构件具有负弯曲强度混杂效应和正弯曲模量混杂效应。可根据碳纤维电阻相对变化率对混杂增强复合材料结构的应变与断裂破坏状态进行实时自感知。研究结果为连续玻璃纤维与碳纤维混杂增强热塑性复合材料结构件的高质高效制造与智能化提供了新工艺与新思路。

Ultrahigh-power electrochemical double-layer capacitors based on structurally integrated 3D carbon tube arrays

The rational design of electrodes is the key to achieving ultrahigh-power performance in electrochemical energy storage devices.Recently,we have constructed well-organized and integrated three-dimensional(3D)carbon tube(CT)grids(3D-CTGs)using a 3D porous anodic aluminum oxide template-assisted method as electrodes of electrical double-layer capacitors(EDLCs),showing excellent frequency response performance.The unique design warrants fast ion migration channels,excellent electronic conductivity,and good structural stability.This study achieved one of the highest carbon-based ultrahigh-power EDLCs with the 3D-CTG electrodes,resulting in ultrahigh power of 437 and 1708 W·cm−3 with aqueous and organic electrolytes,respectively.Capacitors constructed with these electrodes would have important application prospects in the ultrahigh-power output.The rational design and fabrication of the 3D-CTGs electrodes have demonstrated their capability to build capacitors with ultrahighpower performance and open up new possibilities for applications requiring high-power output.

3D Free-Standing Carbon Nanofibers Modified by Lithiophilic Metals Enabling Dendrite-Free Anodes for Li Metal Batteries

Li metal with high-energy density is considered as the most promising anode for the next-generation rechargeable Li metal batteries;however,the growth of Li dendrites seriously hinders its practical application.Herein,3D free-standing carbon nanofibers modified by lithiophilic metal particles(CNF/Me,Me=Sn,Fe,Co)are obtained in situ by the electrospinning method.Benefiting from the lithophilicity,the CNF/Me composite may effectively prevent the formation of Li dendrites in the Li metal batteries.The optimized CNF/Sn–Li composite electrode exhibits a stable cycle life of over 2350 h during Li plating/stripping.When matched with typical commercial LiFePO_(4)(LFP)cathode,the LFP//CNF/Sn–Li full cell presents a high initial discharge specific capacity of 139 mAh g^(−1)at 1 C,which remains at 146 mAh g^(−1)after 400 cycles.When another state-of-the-art commercial LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM(811))cathode is used,the assembled NCM//CNF/Sn–Li full cell shows a large initial specific discharge capacity of 206 mAh g^(−1)at substantially enhanced 10 C,which keeps at the good capacity of 99 mAh g^(−1)after 300 cycles.These results are greatly superior to the counterparts with Li as the anodes,indicating the great potential for practical utilization of the advanced CNF/Sn–Li electrode.

3D Grid of Carbon Tubes with Mn3O4-NPs/CNTs Filled in their Inner Cavity as Ultrahigh-Rate and Stable Lithium Anode

Transition metal oxides are regarded as promising candidates of anode for next-generation lithium-ion batteries(LIBs)due to their ultrahigh theoretical capacity and low cost,but are restricted by their low conductivity and large volume expansion during Li^(+)intercalation.Herein,we designed and constructed a structurally integrated 3D carbon tube(3D-CT)grid film with Mn_(3)O_(4)nanoparticles(Mn_(3)O_(4)-NPs)and carbon nanotubes(CNTs)filled in the inner cavity of CTs(denoted as Mn_(3)O_(4)-NPs/CNTs@3D-CT)as high-performance free-standing anode for LIBs.The Mn_(3)O_(4)-NPs/CNTs@3D-CT grid with Mn_(3)O_(4)-NPs filled in the inner cavity of 3D-CT not only afford sufficient space to overcome the damage caused by the volume expansion of Mn_(3)O_(4)-NPs during charge and discharge processes,but also achieves highly efficient channels for the fast transport of both electrons and Li+during cycling,thus offering outstanding electrochemical performance(865 mAh g^(-1)at 1 A g^(-1)after 300 cycles)and excellent rate capability(418 mAh g^(-1)at 4 A g^(-1))based on the total mass of electrode.The unique 3D-CT framework structure would open up a new route to the highly stable,high-capacity,and excellent cycle and high-rate performance free-standing electrodes for highperformance Li-ion storage.

直写式3D打印碳纤维/碳化硅陶瓷性能优化

在陶瓷制备过程中,烧结工艺至关重要,不仅影响陶瓷的显微组织结构,而且决定着陶瓷的力学性能。因此,为提升碳化硅/碳纤维陶瓷样品的性能,优化烧结工艺。采用直写式3D打印的方式,以碳纤维/碳化硅为打印材料,通过三同轴喷嘴挤出打印,以4种不同的烧结工艺烧结打印的碳纤维/碳化硅陶瓷样品,分析不同烧结工艺对碳纤维/碳化硅陶瓷样品,组织和性能的影响。结果表明:经烧结工艺3,即浸渍液聚碳硅烷与二甲苯的比例为2∶3、以10℃·min^(-1)的升温速率达到烧结温度,烧结后的碳纤维/碳化硅陶瓷样品的组织和性能最好,其致密度可达到95.5%,抗弯强度可达到156 MPa。

碳纳米管修饰3D纤维网基压力传感器的制备及性能

为改善纤维基传感器灵敏度低和响应范围窄等问题,提出了一种以3D纤维网为基材,采用超声辅助浸渍碳纳米管修饰纤维表面,构建出了3D纤维网络结构的压阻式压力传感器。介绍了3D纤维网传感器的制备过程,并对所制备的传感器形貌结构、力学传感性能及应用进行了测试与表征。结果表明:碳纳米管修饰3D纤维网的传感器灵敏度为3.53×10^(-3)kPa^(-1),具有较好的线性度和较高的灵敏度;检测范围达到200 kPa;响应时间和回复时间分别为153 ms和226 ms;经过2000次循环施加压力测试表现出较好的稳定性和耐久性。该传感器能够用于监测人体的运动,如手指弯曲、手腕弯曲、手指点击和脚跟压力等,在可穿戴电子织物领域具有广阔的应用前景。

“碳纤维-石墨烯”混合体系在3D打印聚氨酯复合材料力学及微波后处理工艺中的协同作用

为研究“碳纤维-石墨烯”(carbon fiber-graphene,CF-G)增强热塑性聚氨酯(TPU)复合材料3D打印试件的力学性能以及微波后处理的影响,通过螺杆挤出工艺制备了CF-G增强TPU(G+CF/TPU)复合材料线材,然后采用熔融沉积成型技术和微波后处理工艺,制备了G+CF/TPU复合材料3D打印试件。研究表明,CF-G异质结构能够协同提高TPU复合材料的力学性能,特别是采用新型微波后处理工艺后,G+CF/TPU试件的拉伸强度和韧性得到进一步提高。其原因是CF-G异质结构与微波的协同作用促进了增强相与基体之间的界面黏结,减少了3D打印过程中点、层和道之间的内部缺陷。研究结果对于探索3D打印材料的力学性能强化和后处理工艺优化具有积极的意义。

3D多级孔炭负载铜催化剂及其合成碳酸二甲酯性能研究

以ɑ-纤维素和NaHCO3为原料,采用生物质发泡法制得大孔、介孔和微孔共存的三维(3D)多级孔炭(HPC);以硝酸铜为铜源,通过调变铜负载量制得3D多级孔炭负载铜催化剂(y Cu/HPC),并考察其催化甲醇氧化羰基化合成碳酸二甲酯性能。实验结果表明:当铜负载量(质量分数)为10%时,10Cu/HPC催化剂在DMC合成反应中时空收率(STYDMC)和转换频率(TOF)分别达1778 mg/(g·h)和13.8 s^(-1)。N2吸附、XRD、TEM等表征表明:3D多级孔结构不但有利于铜物种的高度分散,同时可加快底物分子的传质速率,从而提升催化活性。

3D打印碳纳米管/纳米纤维素复合电极制备及性能

本研究探索了基于光固化的3D打印技术制造导电聚合物树脂材料。以可光固化树脂和多壁碳纳米管(MWCNT)混合物为基底,通过添加纳米纤维素(CNF)来改善MWCNT的分散性,使混合树脂达到最佳的导电性能和印刷质量。此外,结合了光固化、热解和化学活化等反应过程,形成可设计的分级孔结构的碳电极,该电极具有从毫米级到微米级再到纳米级分布的孔隙结构,组装对称超级电容器可提供高能量密度0.91 mWh/cm^(2)。

连续碳纤维增强尼龙复合材料的3D打印研究

连续碳纤维增强复合材料具有高强度、刚性、耐磨、耐高温和轻量化等优点,适用于需要高性能且轻量化的领域。将三维(3D)打印技术用于制备连续碳纤维增强复合材料则具有更高效、低成本、高材料利用率和灵活生产等优势。本文开展了连续碳纤维增强尼龙复合材料的3D打印研究,研究了挤出宽度、层厚、打印温度对打印材料拉伸性能以及弯曲性能的影响,并探究了退火后处理对材料力学性能的影响。使用扫描电子显微镜(SEM)观察了3D打印样品的切割横截面和拉伸断裂失效横截面,在不同工艺参数条件下,分析和讨论了打印样品和后处理打印样品的内部结构和力学性能之间的关系。结果表明,当挤出宽度为0.65 mm时打印样品力学性能最佳,拉伸强度和拉伸模量为501.51 MPa和31.70 GPa,弯曲强度和弯曲模量为164.53 MPa和31.91 GPa;当层厚为0.1 mm时打印样品力学性能最佳,拉伸强度和拉伸模量为520.78 MPa和36.59 GPa,弯曲强度和弯曲模量为168.43 MPa和32.31 GPa,之后力学性能随着层厚的增加而减小。打印温度对打印样品的力学影响较小。退火后处理对打印样品的力学性能具有一定的优化效果,拉伸强度提升效果有3.07%,弯曲强度提升了51.27%。

基于连续碳纤维3D打印的结构拓扑优化及工艺研究

本文利用3D打印技术制备了“椭圆形跑道”样件来研究不同纤维角度和纤维层分布对样件机械性能的影响,并通过实验考察各种力学测试中样件的断裂模式。然后基于变密度的拓扑优化理论对三点弯曲梁、C形夹和弹架悬臂进行结构拓扑优化,并通过力学性能实验进行验证。结果表明,在所有的测试中都观察到样件具有各向异性的机械性能,其中纤维方向具有最高的强度和刚度,而跨层方向具有较低的强度和刚度。通过有限元分析和压缩试验表明,经过拓扑优化的连续碳纤维3D打印弹架悬臂结构能够经受住极端运行条件的考验。

基于超声调控浸润性的连续碳纤维复材3D打印研究

为解决3D打印连续碳纤维复合材料(continuous carbon fiber reinforced composites,C-CFRP)成型件内部空隙多、应力集中等缺陷,文章提出了基于熔融沉积技术的超声在线调控打印方法。探究了超声振幅在0μm、10μm、20μm、30μm、40μm、50μm时,C-CFRP丝的拉伸性能,以及超声振幅在0μm、20μm时,C-CFRP件的拉伸、弯曲性能;并通过超景深显微镜观测了CCFRP丝的横截面形貌,以及采用扫描电镜观察了C-CFRP件断裂面的微观结构,最后对超声调控熔融树脂浸润纤维进行了机理分析。结果表明:C-CFRP丝的力学性能随着超声振幅的增加,先提高后降低,在20μm振幅作用下,失效载荷值最大,为121 N,比无超声状态下提高了16%;复材件在20μm振幅作用下,比无超声状态下拉伸性能提高了11%,弯曲性能提高了23%,为高性能C-CFRP 3D打印技术的发展提供了参考。

碳纳米管对3D打印混凝土流变性能及力学性能的影响

碳纳米管(MWCNTs)是一种性能优良的纳米材料,将其掺入3D打印混凝土(3DPC)中不仅会对基体内部微裂纹的生成和扩展以及3D打印混凝土的宏观力学性能产生显著影响,而且会影响新拌3D打印混凝土的流变性能。为了明确碳纳米管对3D打印混凝土性能的影响,通过设置六种碳纳米管掺量(0%、0.01%、0.02%、0.05%、0.08%、0.1%),研究了碳纳米管的掺量对3D打印凝土流变性能及力学性能的影响,并基于SEM测试结果进行了微观分析。研究结果表明:随着碳纳米管掺量的增加,3D打印混凝土的流动度逐渐下降,静态屈服应力、动态屈服应力逐渐增加。各龄期的抗折强度均随着碳纳米管掺量的增加而增大。随碳纳米管掺量的增加,3D打印混凝土的抗压强度先增大后减小,当碳纳米管掺量为0.05%时,其抗压强度最大。SEM结果显示,碳纳米管可以起到桥接和填充作用,能与基体紧密连接,阻止3D打印混凝土内部微裂缝和孔洞的生成与扩展,在较低掺量(不超过0.05%)下即能显著改善3D打印混凝土的微观结构。

基于体素的机械臂连续碳纤维3D打印路径规划

碳纤维长纤3D打印对路径的连续性和复杂构型的无支撑成型均提出了需求。传统三轴熔融沉积3D打印采用平面切片和基于轮廓的路径规划方法,由于成型方向的单一性,悬空结构无法避免支撑的产生;由于采用基于轮廓的路径规划,缺少内部几何信息,无法扩展到曲面空间。针对以上问题,提出了基于机械臂的连续碳纤维3D打印曲面切片和曲面连续路径规划方法。通过三维模型的体素化处理,保证空间信息的完整性;在无支撑无碰撞约束下,分解成系列体素曲面层,保证无支撑成型;采用Fast Marching网格测地线算法,形成曲面空间的连续等距螺旋偏置路径,并对路径进行平滑优化,保证路径的连续性;最后生成用于机械臂3D打印的Gcode路径文件。通过多种三维模型路径规划仿真对比和打印实验,证明了该方法的可行性,实现了曲面分层的无支撑连续路径规划。