Direct growth of ordered N-doped carbon nanotube arrays on carbon fiber cloth as a free-standing and binder-free air electrode for flexible quasi-solid-state rechargeable Zn-Air batteries

The development of an air electrode that is flexible in physical property and highly active and durable at different geometric status for both oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is of crucial importance for the rational design of flexible rechargeable Zn-air batteries(ZABs).Considering their good elasticity,high conductivity,and superior thermal and chemical stability,carbon nanotubes have been widely used as a catalyst support in various electrocatalysts,while oxide or metal nanoparticles have been frequently deposited on the carbon nanotube substrate to perform as the active materials.Considering the poor contact between active materials and carbon nanotubes may introduce a challenge for long-term operating stability,in particular in flexible devices,pure carbon electrocatalyst is highly appreciated.Herein,a free-standing air electrode with cobalt nanoparticles encapsulated N-codoped carbon nanotube arrays uniformly grown on the surface of carbon fiber cloth is developed by a two-step in situ growth method.Such a carbon-based electrode shows outstanding activity for both ORR and OER.The flexible ZAB with such air electrode shows superior flexibility and stability working under extreme bending conditions.Moreover,the polarization and round-trip efficiency for the flexible battery is 0.67 V and 64.4%at 2 mA/cm2,respectively,even after being operated for 30 hours.This study provides a feasible way to design all carbon-based free-standing and flexible electrode and enlightens the electrode design for flexible energy conversion/storage devices.

Investigation on the Formation Mechanism of Double-Layer Vertically Aligned Carbon Nanotube Arrays via Single-Step Chemical Vapour Deposition

The mechanism for the formation of double-layer vertically aligned carbon nanotube arrays(VACNTs) through single-step CVD growth is investigated. The evolution of the structures and defect concentration of the VACNTs are tracked by scanning electron microscopy(SEM) and Raman spectroscopy. During the growth, the catalyst particles are stayed constantly on the substrate. The precipitation of the second CNT layer happens at around 30 min as proved by SEM.During the growth of the first layer, catalyst nanoparticles are deactivated with the accumulation of amorphous carbon coatings on their surfaces, which leads to the termination of the growth of the first layer CNTs. Then, the catalyst particles are reactivated by the hydrogen in the gas flow, leading to the precipitation of the second CNT layer. The growth of the second CNT layer lifts the amorphous carbon coatings on catalyst particles and substrates. The release of mechanical energy by CNTs provides big enough energy to lift up amorphous carbon flakes on catalyst particles and substrates which finally stay at the interfaces of the two layers simulated by finite element analysis. This study sheds light on the termination mechanism of CNTs during CVD process.

Highly Ordered Carbon Nanotube Arrays with Open Ends Grown in Anodic Alumina Nanoholes

Highly ordered multiwalled carbon nanotube arrays were fabricated by pyrolysis of acetylene within anodic alumina templates.Nanotubes are very uniform in diameter and open at both ends. High resolution transmission electron microscopy and electron diffraction analysis show that the carbon nanotubes are well graphitized. These standing and open carbon nanotubes are possible to offer a potential elegant technique for electron emitting devices,chemical functionalization and nanotube composites.

Thermally responsive ionic transport system reinforced by aligned functional carbon nanotubes backbone

Ion transport plays an important role in energy conversion, biosensors, and a variety of biological processes. Carbon nanotubes, especially for the carbon nanotubes arrays with controlled vertically aligned structures, have displayed great potential as a promising material for regulating ion transport behaviors in the applications of the nanofluidic devices and osmotic energy conversion. Herein, we demonstrate the thermo-controlled ion transport system through the vertically aligned multiwall carbon nanotubes arrays membrane modified by the thermo-responsive hydrogel in a simple and reliable way. The functional carbon nanotubes backbone with the inherent surface charge and interstitial channels structure renders the system improved ion transport behaviors and well controlled switching property by thermo. Based on the integrated properties, the energy output from osmotic power in this system could be regulated by the reversible temperature switches. Moreover, it can realize a higher osmotic energy conversion property regulated by the thermos, which may extend the practical application in the future. The system that combines intelligent response with controlled ion transport behaviors and potential osmotic energy utilizations presents a valuable paradigm for the use of carbon nanotubes and hydrogel composite materials and provides a promising way for applications of nanofluidic devices.

Large-area growth of ultra-high-density single-walled carbon nanotube arrays on sapphire surface

A scalable approach to obtaining high-density, large-area single-walled carbon nanotube （SWNT） arrays is essential for realizing the full potential of SWNTs in practical electronic devices; this is still a great challenge. Here, we report an improved synthetic method for large-area growth of ultra-high-density SWNT arrays on sapphire surfaces by combining Trojan catalysts （released from the substrate, to assure ultra-high density） with Mo nanoparticles （loaded on the surface, to stabilize the released Trojan catalysts） as cooperating catalysts. Dense and perfectly aligned SWNTs covered the entire substrate and the local density was as high as 160 tubes/pro. Field-effect transistors （FETs） built on such arrays gave an output current density of -488 μA/μm at the drain-source voltage （Vds） = the gate-source voltage （Vgs） = -2 V, corresponding to an on-conductance per width of 244 μS/μm. These results confirm the wide range of potential applications of Trojan-Mo catalysts in the structure-controlled growth of SWNTs.

Co/N-doped carbon nanotube arrays grown on 2D MOFs-derived matrix for boosting the oxygen reduction reaction in alkaline and acidic media

The development of high-performance and cost-effective electrocatalysts towards oxygen reduction reaction(ORR) is of significant importance,but still challenging for the practical applications in related energy systems.ORR process typically suffers from sluggish kinetics,the exploration of ORR electrocatalyst thus requires elaborate design.Herein,an effective strategy is developed for growing Co/N-doped carbon nanotube arrays on 2D MOFs-derived matrix via the pyrolysis of Co/Zn metalorganic-framework(MOF) nanosheets.The Co/Zn-MOF nanosheets serve as both the self-template for the 2D carbonized framework morphology and C/N source for the in-situ growth of 1D N-doped carbon nanotubes.The constructed hie rarchical architecture effectively integrates the OD/1D Co nanoparticle/Ndoped carbon nanotube interface and 1D(nanotubes)/2D(nanosheets) junction into frameworks with highly exposed active surface,enhanced mass-transport kinetics and electrical conductivity.As a result,the designed composite exhibits superior ORR activity and durability in alkaline media as compared to commercial Pt/C.Particularly,it shows promising ORR performance with a half-wave potential of 0.78 V versus reversible hydrogen electrode and negligible activity attenuation after 5000 potential cycles in acidic electrolyte.The designed strategy can be extended to construct other MOFs-derived carbon matrixes with diverse hierarchical structures and provide an efficient avenue for searching highperformance electrocatalysts.

A Highly Ordered Hydrophilic–Hydrophobic Janus Bi-Functional Layer with Ultralow Pt Loading and Fast Gas/Water Transport for Fuel Cells

One of the critical challenges that limit broad commercialization of proton exchange membrane fuel cells(PEMFC)is to reduce the usage of Pt while maintaining high power output and sufficient durability.Herein,a novel bifunctional layer consisting of vertically aligned carbon nanotubes(VACNTs)and nanoparticles of Pt-Co catalysts(Pt-Co/VACNTs)is reported for highperformance PEMFCs.Readily prepared by a two-step process,the Pt-Co/VACNTs layer with a hydrophilic catalyst-loaded side and a hydrophobic gas diffusion side enables a PTFE-free electrode structure with fully exposed catalyst active sites and superior gas–water diffusion capability.When tested in a PEMFC,the bi-functional Pt-Co/VACNTs layer with ultralow Pt loading(~65μgcathodecm-2)demonstrates a power density of 19.5 kW gPt cathode-1 at 0.6 V,more than seven times that of a cell with commercial Pt/C catalyst(2.7 kW gPt cathode-1 at 0.6 V)at a loading of 400μgcathodecm-2 tested under similar conditions.This remarkable design of VACNTs-based catalyst with dual functionalities enables much lower Pt loading,faster mass transport,and higher electrochemical performance and stability.Further,the preparation procedure can be easily scaled up for low-cost fabrication and commercialization.

Encapsulated carbon nanotube array as a thermal interface material compatible with standard electronics packaging

Vertically aligned carbon nanotubes arrays(VACNTs)are a promising candidate for the thermal interface material(TIM)of next-generation electronic devices due to their attractive thermal and mechanical properties.However,the environment required for synthesizing VACNTs is harsh and severely incompatible with standard device packaging processes.VACNTs’extremely low in-plane thermal conductivity also limits its performance for cooling hot spots.Here,using a transfer-and-encapsulate strategy,a two-step soldering method is developed to cap both ends of the VACNTs with copper microfoils,forming a standalone Cu-VACNTs-Cu sandwich TIM and avoiding the need to directly grow VACNTs on chip die.This new TIM is fully compatible with standard packaging,with excellent flexibility and high thermal conductivities in both in-plane and through-plane directions.The mechanical compliance behavior and mechanism,which are critical for TIM applications,are investigated in depth using in situ nanoindentation.The thermal performance is further verified in an actual light emitting diode(LED)cooling experiment,demonstrating low thermal resistance,good reliability,and achieving a 17℃ temperature reduction compared with state-of-the-art commercial TIMs.This study provides a viable solution to VACNTs’longstanding problem in device integration and free-end contact resistance,bringing it much closer to application and solving the critical thermal bottleneck in next-generation electronics.

MWCNTs based flexible and stretchable strain sensors

Carbon nanotubes have potential applications in flexible and stretchable devices due to their remarkable electromechanical properties.Flexible and stretchable strain sensors of multi-walled carbon nanotubes（MWCNTs）with aligned or random structures were fabricated on poly-dimethylsiloxane（PDMS） substrate with different techniques.It was observed that the spraycoatedtechniquebased strain sensor fabricated on PDMS substrate showed higher sensitivity higher stretchability,better linearity and excellent longer time stability than the sensor fabricated with other methods presented in this work.The scanning electron microscopy images indicated the spray coating technique can produce a better uniform and compact CNT network,which is the important role affecting the performance of CNT-based flexible strain sensors.