High-performance proton exchange membrane fuel cell with ultra-low loading Pt on vertically aligned carbon nanotubes as integrated catalyst layer

Reducing a Pt loading with improved power output and durability is essential to promote the large-scale application of proton exchange membrane fuel cells(PEMFCs).To achieve this goal,constructing optimized structure of catalyst layers with efficient mass transportation channels plays a vital role.Herein,PEMFCs with order-structured cathodic electrodes were fabricated by depositing Pt nanoparticles by Ebeam onto vertically aligned carbon nanotubes(VACNTs)growth on Al foil via plasma-enhanced chemical vapor deposition.Results demonstrate that the proportion of hydrophilic Pt-deposited region along VACNTs and residual hydrophobic region of VANCTs without Pt strongly influences the cell performance,in particular at high current densities.When Pt nanoparticles deposit on the top depth of around 600 nm on VACNTs with a length of 4.6μm,the cell shows the highest performance,compared with others with various lengths of VACNTs.It delivers a maximum power output of 1.61 W cm^(-2)(H_(2)/O_(2),150 k Pa)and 0.79 W cm^(-2)(H_(2)/Air,150 k Pa)at Pt loading of 50μg cm^(-2),exceeding most of previously reported PEMFCs with Pt loading of<100μg cm^(-2).Even though the Pt loading is down to 30μg cm^(-2)(1.36 W cm^(-2)),the performance is also better than 100μg cm^(-2)(1.24 W cm^(-2))of commercial Pt/C,and presents better stability.This excellent performance is critical attributed to the ordered hydrophobic region providing sufficient mass passages to facilitate the fast water drainage at high current densities.This work gives a new understanding for oxygen reduction reaction occurred in VACNTs-based ordered electrodes,demonstrating the most possibility to achieve a substantial reduction in Pt loading<100μg cm^(-2) without sacrificing in performance.

A comparison of the field emission characteristics of vertically aligned graphene sheets grown on different SiC substrates

The field emission （FE） properties of vertically aligned graphene sheets （VAGSs） grown on different SiC substrates are reported. The VAGSs grown on nonpolar SiC （10-10） substrate show an ordered alignment with the graphene basal plane-parallel to each other, and show better FE features, with a lower turn-on field and a larger field enhancement factor. The VAGSs grown on polar SiC （000-1 ） substrate reveal a random petaloid-shaped arrangement and stable current emission over 8 hours with a maximum emission current fluctuation of only 4%. The reasons behind the differing FE characteristics of the VAGSs on different SiC substrates are analyzed and discussed.

Freeze-assisted Tape Casting of Vertically Aligned MXene Films for High Rate Performance Supercapacitors

Conventional electrode preparation techniques of supercapacitors such as tape casting or vacuum filtration often lead to the restacking or agglomeration of twodimensional(2 D)materials.As a result,tortuous paths are created for the electrolyte ions and their adsorption onto the surfaces of the active materials can be prevented.Consequently,maintaining high rate performance while increasing the thickness of electrodes has been a challenge.Herein,a facile freeze-assisted tape-casting(Fa TC)method is reported for the scalable fabrication of flexible MXene(Ti3C2Tx)supercapacitor electrode films of up to 700μm thickness,exhibiting homogeneous ice-template microstructure composed of vertically aligned MXene walls within lamellar pores.The efficient ion transport created by the internal morphology allows for fast electrochemical charge–discharge cycles and near thickness-independent performance at up to 3000 m V s-1 for films of up to 300μm in thickness.By increasing the scan rate from 20 to 10,000 m V s-1,Ti3C2Tx films of 150μm in thickness sustain 50%of its specific capacitance(222.9 F g-1).When the film thickness is doubled to 300μm,its capacitance is still retained by 60%(at 213.3 F g-1)when the scan rate is increased from 20 to3000 m V s-1,with a capacitance retention above 97.7%for over 14,000 cycles at10 A g-1.They also showed a remarkably high gravimetric and areal power density of 150 k W kg-1 at 1000 A g-1 and 667 m W cm-2 at 4444 m A cm-2,respectively.Fa TC has the potential to provide industry with a viable way to fabricate electrodes formed from 2 D materials on a large scale,while providing promising performance for use in a wide range of applications,such as flexible electronics and wearable energy 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.

Vertically Aligned Silicon Carbide Nanowires/Boron Nitride Cellulose Aerogel Networks Enhanced Thermal Conductivity and Electromagnetic Absorbing of Epoxy Composites

With the innovation of microelectronics technology, the heat dissipation problem inside the device will face a severe test. In this work, cellulose aerogel(CA) with highly enhanced thermal conductivity(TC) in vertical planes was successfully obtained by constructing a vertically aligned silicon carbide nanowires(SiC NWs)/boron nitride(BN) network via the ice template-assisted strategy. The unique network structure of SiC NWs connected to BN ensures that the TC of the composite in the vertical direction reaches 2.21 W m^(-1) K^(-1) at a low hybrid filler loading of 16.69 wt%, which was increased by 890% compared to pure epoxy(EP). In addition, relying on unique porous network structure of CA, EP-based composite also showed higher TC than other comparative samples in the horizontal direction. Meanwhile, the composite exhibits good electrically insulating with a volume electrical resistivity about 2.35 × 10^(11) Ω cm and displays excellent electromagnetic wave absorption performance with a minimum reflection loss of-21.5 dB and a wide effective absorption bandwidth(<-10 dB) from 8.8 to 11.6 GHz. Therefore, this work provides a new strategy for manufacturing polymer-based composites with excellent multifunctional performances in microelectronic packaging applications.

Self-assembled all-oxides three-phase vertically aligned nanocomposite thin film with multifunctionality

Multi-phase vertically aligned nanocomposite(MP-VAN)thin films represent a promising avenue for achieving complex multifunctionality,exploring novel interfacial phenomena,and enabling complex metamaterial designs and exploration.In this study,a novel self-assembled all-oxides three-phase VAN system was conceptualized and fabricated utilizing pulsed laser deposition(PLD)with a single composite target.Detailed microstructural analysis reveals the presence of three distinct phases:LiNbO_(3),CeO_(2-x),and LiNbCe_(1-x)O_(y)within the MP-VAN films.Subsequently,ferroelectric,dielectric,optical anisotropy,and magnetic properties were systematically investigated to showcase the multifunctionality inherent in these films.This work presents a pioneering approach to designing and realizing MP-VAN systems,and opens up opportunities for tailoring the complex three-dimensional(3D)physical properties and property coupling of VAN films towards diverse device applications.

Template-assisted growth of Co-BaTiO_(3) vertically aligned nanocomposite thin films with strong magneto-optical coupling effect

Oxide-metal based nanocomposite thin films have attracted great interests owing to their unique anisotropic structure and physical properties.A wide range of Au-based oxide-metal nanocomposites have been demonstrated,while other metal systems are scarce due to the challenges in the initial nucleation and growth as well as possible interdiffusions of the metallic nanopillars.In this work,a unique anodic aluminum oxide(AAO)template was used to grow a thin Co seed layer and the following self-assembled metal-oxide(Co-BaTiO_(3))vertically aligned nanocomposite thin film layer.The AAO template allows the uniform growth of Co-seeds and successfully deposition of highly ordered Co pillars(with diameter<5 nm and interval between pillars<10 nm)inside the oxide matrix.Significant magnetic anisotropy and strong magneto-optical coupling properties have been observed.A thin Au-BaTiO_(3) template was also later introduced for further enhanced nucleation and ordered growth of the Co-nanopillars.Taking the advantage of such a unique nanostructure,a large out-of-plane(OP)coercive field(Hc)of~5000 Oe has been achieved,making the nanocomposite an ideal candidate for high density perpendicular magnetic tunneling junction(p-MTJ).A strong polar magneto-optical Kerr effect(MOKE)has also been observed which inspires a novel optical-based reading method of the MTJ states.

3D vertically aligned microchannel structure to enhance piezoelectric energy harvesting performance of PZT/PVDF&CNTs piezoelectric composites

Piezoelectric energy harvesters(PEHs)have attracted significant attention with the ability of converting mechanical energy into electrical energy and power the self-powered microelectronic components.Generally,material's superior energy harvesting performance is closely related to its high transduction coefficient(d_(33)×g_(33)),which is dependent on higher piezoelectric coefficient d33 and lower dielectric constantεr of materials.However,the high d33 and lowεr are difficult to be simultaneously achieved in piezoelectric ceramics.Herein,lead zirconate titanate(PZT)based piezoelectric composites with vertically aligned microchannel structure are constructed by phase-inversion method.The polyvinylidene fluoride(PVDF)and carbon nanotubes(CNTs)are mixed as fillers to fabricate PZT/PVDF&CNTs composites.The unique structure and uniformly distributed CNTs network enhance the polarization and thus improve the d33.The PVDF filler effectively reduce theεr.As a consequence,the excellent piezoelectric coefficient(d_(33)=595 pC/N)and relatively low dielectric constant(ε_(r)=1,603)were obtained in PZT/PVDF&CNTs composites,which generated an ultra-high d_(33)×g_(33) of 24,942×10^(−15) m^(2)/N.Therefore,the PZT/PVDF&CNTs piezoelectric composites achieve excellent energy harvesting performance(output voltage:66 V,short current:39.22μA,and power density:1.25μW/mm^(2)).Our strategy effectively boosts the performance of piezoelectric-polymer composites,which has certain guiding significance for design of energy harvesters.

Vertically aligned W(Mo)S_(2)/N-W(Mo)C-based light-assisted electrocatalysis for hydrogen evolution in acidic solutions

The development of non-noble-metal hydrogen evolution electrocatalysts holds great promises for a sustainable energy system.Here,a hybrid W(Mo)S_(2)/NW(Mo)C nanosheet with array structures was reported for an efficient light-as sis ted hydrogen evolution electrocatalysts in acidic solutions.The resulting vertically aligned W(Mo)S_(2)/N-W(Mo)C was supported on a conductive carbon fiber paper,which can be produced through annealing W(Mo)S_(2)nanosheets by simultaneous carbonization and N-doping in Ar/H_(2)atmosphere.This optimized WS_(2)/NWC and MoS_(2)/N-MoC electrode exhibits remarkable lightassisted electrocatalysis activity with overpotentials of0.120 and 0.122 V at 10 mA·cm^(-1)in acidic solutions,respectively.Such high hydrogen evolution activities should be attributed to the electrocatalytic synergistic effects of the abundant active sites existing in different phase boundaries and the absorption for ultraviolet-visible light.This study shows that synthesis of low-cost and highly active W(Mo)S_(2)-based hydrogen evolution electrocatalyst opens up a route toward the development of scalable production of hydrogen fuels.

Binder-free Li-O_(2)battery cathodes using Ni-and PtRu-coated vertically aligned carbon nanofibers as electrocatalysts for enhanced stability

The development of an ideal cathode for Li-O_(2)battery(LOB)has been a great challenge in achieving high discharge capacity,enhanced stability,and longevity.The formation of undesired and irreversible discharge products on the surface of current cathode materials limit the life span of the LOB.In this study,we report the systematic electrochemical study to compare the performance of LOB employing a unique graphitic nanostructured carbon architecture,i.e.,vertically aligned carbon nanofiber(VACNF)arrays,as the cathode materials.Transition metal(Ni)and noble metal alloy(PtRu)are further deposited on the VACNF array as electrocatalysts to improve the discharge/charge processes at the cathode.The structure of as-prepared electrodes was examined with the field emission scanning electron microscopy,high-resolution transmission electron microscopy,and X-ray photoelectron spectroscopy(XPS).The LOB with VACNF-Ni electrode delivered the highest specific and areal discharge capacities(14.92 Ah·g^(−1),4.32 mAh·cm^(−2))at 0.1 mA·cm^(−2)current density as compared with VACNF-PtRu(9.07 Ah·g^(−1),2.62 mAh·cm^(−2)),bare VACNF(5.55 Ah·g^(−1),1.60 mAh·cm^(−2))and commercial Vulcan XC(3.83 Ah·g^(−1),1.91 mAh·cm^(−2)).Cycling stability tests revealed the superior performance of VACNF-PtRu with 27 cycles as compared with VACNF-Ni(13 cycles),VACNF(8 cycles),and Vulcan XC(3 cycles).The superior cycling stability of VACNF-PtRu can be attributed to its ability to suppress the formation of Li2CO3 during the discharge cycle,as elucidated by XPS analysis of discharged samples.We also investigated the impact of carbon cloth and carbon fiber as cathode electrode substrate on the performance of LOB.

Vertically aligned nanocomposite films by self-assembled epitaxial nucleation for super-broadband transparent conductors

Designing super-broadband transparent conductors is challenging because of the exclusive nature of conductivity and infrared transmittance.Here,using a one-step process,we created vertically aligned nanocomposite conducting films with high transparency across a super-broad wavelength range.Vertically aligned transparent Ba_(3)V_(2)O_(8)nanocolumns with lateral-100-nm widths enable high transmittance(>50%,even at a 4-μm wavelength)for all incident light and outperform that of Sn-doped In_(2)O_(3),while the conducting SrVO_(3)matrix retains low resistivity(<0.56 mΩcm at room temperature).A combined study of scanning transmission electron microscopy,scattering scanning nearfield infrared microscopy,and X-ray diffraction revealed that spontaneous phase separation of Ba_(3)V_(2)O_(8)nanocolumns in a SrVO_(3)matrix film occurs via self-assembled epitaxial nucleation.Our vertically aligned nanocomposite films provide a fertile platform for next-generation optoelectronics.

Vertically aligned Ni/NiO nanocomposites with abundant oxygen deficient hetero-interfaces for enhanced overall water splitting

The design of heterostructured transition metal-based electrocatalysts with controlled composition and interfaces is key to increasing the efficiency of the water electrolysis and the elucidation of reaction mechanisms.In this work,we report the synthesis of well-controlled vertically aligned Ni/NiO nanocomposites consisting of Ni nanoclusters embedded in NiO,which result in highly efficient electrocatalysts for overall water splitting.We show that such a high catalytic efficiency toward both the hydrogen evolution reaction(HER)and the oxygen evolution reaction(OER)originates from a synergetic effect at Ni/NiO interfaces that significantly reduces the energy barrier for water dissociation,and favours the formation of reactive H*intermediates on the Ni side of the interface,and OH_(ads) on the NiO side of the interface.A study of water chemisorption based on near-ambient pressure photoelectron spectroscopy indicates that the abundant hetero-interfaces in Ni/NiO nanocomposite promote the dissociation of water with a three-fold increase in the surface concentration of OH_(ads) compared with pure NiO.Density functional theory calculations indicate that Ni/NiO interface leads to the reduction of the water dissociation energy barrier due to a high concentration of oxygen vacancies at NiO side of the interface,whereas the formation of highly active metallic Ni sites with an optimal value of Gibbs free energy of H*(ΔG_(H*)=−0.16 eV)owes to a favourable adjustment of the electron energetics at the interface,thus accelerating the overall electrochemical water splitting.

Novel vertically aligned nanocomposite of Bi_(2)WO_(6)-Co_(3)O_(4) with room-temperature multiferroic and anisotropic optical response

A new vertically aligned nanocomposite(VAN)structure based on two-dimensional(2D)layered oxides has been designed and self-assembled on both LaAlO_(3)(001)and SrTiO3(001)substrates.The new VAN structure consists of epitaxially grown Co_(3)O_(4) nanopillars embedded in the Bi_(2)WO_(6) matrix with a unique 2D layered structure,as evidenced by the microstructural analysis.Physical property measurements show that the new Bi_(2)WO_(6)-Co_(3)O_(4) VAN structure exhibits strong ferromagnetic and piezoelectric response at room temperature as well as anisotropic permittivity response.This work demonstrates a new approach in processing multifunctional VANs structure based on the layered oxide systems towards future nonlinear optics,ferromagnets,and multiferroics.

Low Temperature Growth of Vertically Aligned Carbon Nanotubes via Floating Catalyst Chemical Vapor Deposition Method

Synthesis of carbon nanotubes （CNTs） below 600℃ using supporting catalyst chemical vapor deposition method was reported by many research groups. However, the floating catalyst chemical vapor deposition received less attention due to imperfect nanotubes produced. In this work, the effects of varying the preheating temperature on the synthesis of CNT were investigated. The reaction temperature was set at 570℃. The preheating set temperature was varied from 150 to 400℃ at 50℃ interval. Three O-ring shape heating mantels were used as heating source for the preheater. In situ monitoring device was used to observe the temperature profile in the reactor. Benzene and ferrocene were used as the carbon source and catalyst precursor, respectively. Vertically aligned CNTs were synthesized when the preheating temperature was set at 400℃. When the preheating temperature was increased up to 400℃, both the length and the alignment of CNTs produced were improved.

Ultralow Interfacial Thermal Resistance of Graphene Thermal Interface Materials with Surface Metal Liquefaction

Developing advanced thermal interface materials(TIMs)to bridge heat-generating chip and heat sink for constructing an efficient heat transfer interface is the key technology to solve the thermal management issue of high-power semiconductor devices.Based on the ultra-high basal-plane thermal conductivity,graphene is an ideal candidate for preparing high-performance TIMs,preferably to form a vertically aligned structure so that the basal-plane of graphene is consistent with the heat transfer direction of TIM.However,the actual interfacial heat transfer efficiency of currently reported vertically aligned graphene TIMs is far from satisfactory.In addition to the fact that the thermal conductivity of the vertically aligned TIMs can be further improved,another critical factor is the limited actual contact area leading to relatively high contact thermal resistance(20-30 K mm^(2) W^(−1))of the“solid-solid”mating interface formed by the vertical graphene and the rough chip/heat sink.To solve this common problem faced by vertically aligned graphene,in this work,we combined mechanical orientation and surface modification strategy to construct a three-tiered TIM composed of mainly vertically aligned graphene in the middle and micrometer-thick liquid metal as a cap layer on upper and lower surfaces.Based on rational graphene orientation regulation in the middle tier,the resultant graphene-based TIM exhibited an ultra-high thermal conductivity of 176 W m^(−1) K^(−1).Additionally,we demonstrated that the liquid metal cap layer in contact with the chip/heat sink forms a“liquid-solid”mating interface,significantly increasing the effective heat transfer area and giving a low contact thermal con-ductivity of 4-6 K mm^(2) W^(−1) under packaging conditions.This finding provides valuable guidance for the design of high-performance TIMs based on two-dimensional materials and improves the possibility of their practical application in electronic thermal management.

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.

A Study on the Effects of Carrier Gases on the Structure and Morphology of Carbon Nanotubes Prepared by Pyrolysis of Ferrocene and C_2H_2 Mixture

Carbon nanotubes （CNTs） were prepared using different carrier gases, with ferrocene as the catalyst precusor and acetylene as the carbon source. The effects of ammonia and nitrogen as carrier gases on the structure and morphology of CNTs were investigated. Transmission electron microscope （TEM）, high-resolution electron microscope （HRTEM）, scanning electron microscope （SEM） and X-ray diffraction （XRD） were employed to characterize the products and the catalyst. Experiment results show that the CNTs grown in N2 gas exhibited cylindrical and tubular structure, while a bamboo-like structure was observed for the CNTs grown in NH3 gas. Moreover, vertically aligned CNTs were obtained on an A12O3 disk when NH3 was used as the carrier gas. The carrier gas also exerted influence on the shape of the catalyst. Based on the theory of active centers of catalysis and combined with the particle shape of the catalyst, a growth model for the vertically aligned CNTs on the substrate is given.

Aligned carbon nanotubes for lithium-ion batteries:A review

Nanoscale materials are gaining massive attention in recent years due to their potential to alleviate the present electrochemical electrode constraints.Possessing high conductivity(both thermally and electrically),high chemical and electrochemical stability,exceptional mechanical strength and flexibility,high specific surface area,large charge storage capacity,and excellent ionadsorption,carbon nanotubes(CNTs)remain one of the most researched of other nanoscale materials for electrochemical energy storage.Rather than having them packed at random,CNTs perform better when packed/grown to order,vertically or horizontally aligned to a substrate.This study presents an overview of the impact of CNT alignment on the electrochemical performance of lithium-ion batteries(LIBs).The unique properties of vertically aligned CNTs(VACNTs)for LIB application were discussed.Furthermore,the mechanisms of charge storage and electrochemical performances in VACNT-based(pristine and composites)anodes and cathodes of LIBs were succinctly reviewed.In the end,the existing challenges and future directions in the field were also briefly discussed.

Vertical Alignment of Anisotropic Fillers Assisted by Expansion Flow in Polymer Composites

Orientation control of anisotropic one-dimensional(1D)and two-dimensional(2D)materials in solutions is of great importance in many fields ranging from structural materials design,the thermal management,to energy storage.Achieving fine control of vertical alignment of anisotropic fillers(such as graphene,boron nitride(BN),and carbon fiber)remains challenging.This work presents a universal and scalable method for constructing vertically aligned structures of anisotropic fillers in composites assisted by the expansion flow(using2D BN platelets as a proof-of-concept).BN platelets in the silicone gel strip are oriented in a curved shape that includes vertical alignment in the central area and horizontal alignment close to strip surfaces.Due to the vertical orientation of BN in the central area of strips,a throughplane thermal conductivity as high as 5.65 W m^(-1) K^(-1) was obtained,which can be further improved to 6.54 W m^(-1) K^(-1) by combining BN and pitch-based carbon fibers.The expansion-flow-assisted alignment can be extended to the manufacture of a variety of polymer composites filled with 1D and 2D materials,which can find wide applications in batteries,electronics,and energy storage devices.

Synthesis of novel aromatic polyimides containing bulky side chain for vertical alignment liquid crystals

In this study, a novel 4-（4-octyloxybenzoyloxy）biphenyl-3′,5′-diaminobenzoate and polyimides based on it were synthesized. The polyimide with mesogenic unit side chain exhibited excellent vertical alignment for nematic liquid crystal （LC）. The pretilt angles of LCs above 89° were kept after the rubbing process with 220 mm rubbing strength. The polyimide films as the alignment layer were baked at 120℃ for 12 h, the vertical alignment of LCs was still uniform and stable. Meanwhile, the UV-vis spectra of the noyel polyimide films showed the high transparency in a visible wave length.