Macroscale evaluation and testing of chemically hydrogenated graphene for hydrogen storage applications

The effective storage of H₂ gas represents one of the major challenges in the wide spread adoption of hydrogen powered fuel cells for light vehicle transportation. Here, we investigate the merits of chemically hydrogenated graphene (graphane) as a means to store high-density hydrogen fuel for on demand delivery. In order to evaluate hydrogen storage at the macroscale, 75 g of hydrogenated graphene was synthesized using a scaled up Birch reduction, representing the largest reported synthesis of this material to date. Covalent hydrogenation of the material was characterized via Raman spectroscopy, X-ray diffraction (XRD), and thermogravimetric analysis (TGA). We go on to demonstrate the controlled release of H₂ gas from the bulk material using a sealed pressure reactor heated to 600 °C, identifying a bulk hydrogen storage capacity of 3.2 wt%. Additionally, we demonstrate for the first time, the successful operation of a hydrogen fuel cell using chemically hydrogenated graphene as a power source. This work demonstrates the utility of chemically hydrogenated graphene as a high-density hydrogen storage medium, and will be useful in the design of prototype hydrogen storage systems moving forward.     

用于水质净化的氧化石墨烯膜研究进展

氧化石墨烯膜具有超高的水通量、可控的层间距以及卓越的分离性能，这些优异的特性使氧化石墨烯膜有望成为新一代膜材料并用于水环境中物质的精确分离。对氧化石墨烯膜的研究已经取得了许多重要的成果，本文系统地阐述了用于水质净化的氧化石墨烯膜的结构特性和构效关系，总结了氧化石墨烯膜典型的制备方法，重点介绍了氧化石墨烯膜的改性方式，概述了氧化石墨烯膜在多种水环境中的应用，总结并展望了氧化石墨烯膜的发展方向，为设计和合成高性能氧化石墨烯膜用于水质净化提供新的思路。     

Two/three-dimensional reduced graphene oxide coating for porous flow distributor in polymer electrolyte membrane fuel cell

There are drawbacks to use stainless-steel plates as a flow distributor plate in fuel cell, due to some of their properties being inferior to graphite flow distributor plates in terms of electrical conductivity and corrosion resistance. To overcome these problems, many researches have been conducted to improve the properties of stainless-steel flow distributor plates through coating of carbon materials. Herein, two-dimensional Web-like graphene (WG) and self-assembled three-dimensional graphene (STG) are coated through superheat vaporization of micro-droplet method. WG is coated in porous Ni–Cr foam and STG is constructed on the flat flow distributor plate, and they exhibit the feasibility to be applied in flow distributors. Compared to uncoated Ni–Cr foam, the performance of the PEMFC system with the graphene coated foam is enhanced remarkably. Furthermore, the flow distributor plate with the STG exhibits potential to be used directly to flow distributor.     

Graphene-based polymer composites with ultra-high in-plane thermal conductivity: A comparison study between optothermal Raman spectroscopy and laser flash method

We developed a simple solution mixing and molding process for the incorporation of graphene nano-flakes (GNFs) in polymer films. Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and poly(ethylene-co-methacrylic acid) (PEMAA) were used for preparation of the samples. The orientation and stacking of GNFs were confirmed using a scanning electron microscope. The thermal conductivity values for these composites were obtained using (1) laser flash method (commercially available) and (2) an optothermal Raman (OTR) technique (homemade device). The former measures the thermal diffusivity (α) and one needs to measure the density (ρ) and the heat capacity (C_p) of the composites in order to measure the in-plane thermal conductivity (κ = α.ρ.C_p), while the latter measures the in-plane thermal conductivity directly from the relation between the excitation power and the position of the Raman resonance. The data obtained from Raman spectroscopy were analyzed, assuming heat propagation in three and two dimensions. The Raman results obtained based on the two-dimensional model were very close to the results obtained using the laser flash method with less than 10% difference. The OTRspectroscopy was found to be a promising technique for measuring the in-plane thermal conductivity of carbon-based polymer composites. PVDF-HFP and PEMAA composite films with very high in-plane thermal conductivity (25 W m⁻¹ K⁻¹) were obtained through the incorporation of GNFs (20 wt % concentration). Considering a very low thermal conductivity of these polymers (<0.2 W m⁻¹ K⁻¹), this corresponds to a large enhancement of roughly 12 400%. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48927.     

High-performance sodium polyacrylate nanocomposites developed by using ionic liquid covalently modified multiwalled carbon nanotubes

Ionic liquids grafted with multiwalled-nanotubes (CNT Br/NTf₂), involving hydrophilic bromide salt and hydrophobic bis(trifluoromethanesulphonyl)imide salt, were prepared by amidation, followed by an easy solution-casting method of blending CNT Br/NTf₂ with sodium polyacrylate (PAA) as well as crosslinking agent (XR-100) to form PAA hybrid nanocomposites. The uniform dispersion of CNT Br/NTf₂ were analyzed by TEM. The defects and physical properties of fillers were characterized by Raman spectroscopy, Contact angle test, and TGA. Furthermore, microstructures of hybrid nanocomposites were characterized by SEM, from which it can be found that fillers were homogeneously distributed in the PAA matrix. CNT Br/NTf₂ significantly improved the mechanical properties and tensile fatigue resistance, as well as offered tunable swelling behavior of PAA nanocomposites without wasting too much of thermal stability. This study offers a simple approach to develop multifunctional materials based on ionic liquids covalently modified MWCNTs PAA nanocomposites.     

Poly(vinyl alcohol) foams reinforced with carbon nanotubes for stapedial annular ligament applications

This study aims to develop carbon nanotubes (CNTs) reinforced poly(vinyl alcohol) (PVA) foams as a possible material for stapedial annular ligament (SAL) application. As-grown (AG) and purified CNTs are used as reinforcing fillers for PVA foams. Uniaxial and cyclic compression tests reveal that specific modulus and energy dissipation behavior improve after reinforcing foam with CNTs. A relatively higher improvement in specific modulus is recorded for purified CNTs as they tend to produce stiffer cell walls. Thermogravimetric analysis shows thermal stability improves after addition of CNTs in PVA foams. The 50 wt % degradation temperature is higher for PVA_AG foam in comparison to neat PVA foam. Under dynamic loading storage, modulus is found to be higher for CNT doped foams with higher relative improvement with purified CNTs than AG CNTs. It is shown that reinforcing PVA foams with purified CNTs is a feasible strategy to improve their average mechanical properties and microstructure for SAL application. While the specific elastic modulus of neat PVA foam found to be in range of 0.05–0.06 MPa gcc⁻¹ with almost zero porosity. The addition of CNTs provides a wide range of specific elastic modulus 0.1–1.3 MPa gcc⁻¹ with an average pores size of about 300 μm. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48736.     

石墨烯热电器件栅控特性研究

为了获得一种稳定可控的能源，提出一种栅控石墨烯热电器件。通过对石墨烯通道的载流子输运机理的分析，获得了温度和栅压对通道电阻的影响。依据半经典Mott公式推导了石墨烯塞贝克系数的表达式，同时给出了石墨烯的电导率和热导率模型。最后通过有限元分析(FEA)建模获得不同栅压条件下的器件温度，当栅极电压V_B=0 V时，石墨烯热电器件热端和冷端温度差为30 K；当V_B=6 V时，最大温差达到50 K；当V_B=30 V时，最小温差只有10 K。结果表明，栅压对热电器件的性能有明显的调控性。该研究可为石墨烯热电器件的设计提供理论参考。     

Decorating surface charge of graphite nanoplate using an electrostatic coupling agent for 3-dimensional polymer nanocomposite

Here, we report a facile approach to electrostatically couple the surface charges of graphite nanoplate (GNP) fillers and poly(methyl methacrylate) (PMMA) polymer particles using ethylene maleic anhydride (EMA) copolymer as an electrostatic coupling agent. Our strategy involved switching the intrinsic repulsive electrostatic interactions between the directly exfoliated GNPs fillers and the PMMA particles to attractive electrostatic surface interactions for preparing core(PMMA)-shell (GNP) precursor in order to optimizing 3-dimensionally dispersed polymer nanocomposite. As a result, the electrical conductivity of the composites dramatically increased by a factor of 16.7 in the EMA-coupled GNP/PMMA composites compared with that of the EMA-free GNP/PMMA composites. In addition, the percolation threshold was also notably reduced from 0.32 to 0.159 vol% after electrostatic coupling of the GNPs fillers and PMMA particles. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48390.     

Reversible Na+-extraction/insertion in nitrogen-doped graphene-encapsulated Na3V2(PO4)2F3@C electrode for advanced Na-ion battery

NASICON-structured sodium vanadium fluorophosphate has caused widespread concern for sodium energy conversion and storage because of its high voltage platform and high theoretical energy density. However, the inferior electrical conductivity is still a big problem, which greatly prevent the applications of Na₃V₂(PO₄)₂F₃ material. Herein, the nitrogen-doped graphene-encapsulated Na₃V₂(PO₄)₂F₃@C (NG-NVPF@C) has been prepared using the sol-gel approach. The physical and electrochemical performances for the resulted NG-NVPF@C composite have been systematically characterized and compared with that of Na₃V₂(PO₄)₂F₃@C (NVPF@C) in this study. The electrochemical tests demonstrate that the as-fabricated NG-NVPF@C displays higher capacity, superior rate property and better cyclic life than NVPF@C. It displays the discharge capacity of 108.6 mAh g⁻¹ at 5C. Moreover, it also possesses the high capacity of 101.6 mAh g⁻¹ at 10C over 300 cycles with the capacity retention of about 96.5%. The improved properties of NG-NVPF@C electrode are assigned to the constructed conductive network by nitrogen-doped graphene, which can modify the conductivity of Na₃V₂(PO₄)₂F₃.     

P doped CoMoO4/RGO as an efficient hybrid catalyst for hydrogen evolution

Transition metal oxides, as newly earth-abundant and low-cost catalysts, have been regarded as promising materials for electrocatalytic oxygen evolution. However, they are rarely used as an electrocatalyst in hydrogen evolution reaction (HER) due to the poor HER activity. Herein, we present a facile two-step method to synthesize P doped CoMoO₄/RGO (P-CoMoO₄/RGO) with different atomic ratios of Co²⁺/Co³⁺ through a simple phosphorization strategy by changing the mass of NaH₂PO₂. The effective P-doping into CoMoO₄/RGO can modify the electronic properties and modulate the atomic ratio of Co²⁺/Co³⁺, which promotes the electron transfer and creates more activity sites. Therefore, the optimized P-CoMoO₄/RGO with a relatively larger atomic ratio of Co²⁺/Co³⁺ shows superior HER performances in alkaline media, which affords a current density of 10 mA cm⁻² at a small overpotential of 90 mV and a low Tafel slope of 62 mV dec⁻¹ along with having satisfactory long-term stability. This work provides a valuable route to enhance the HER activity of transition metal oxides.