Browsing by Author "Gandomi, Yasser Ashraf"

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Amino-functionalization on graphene oxide sheets using an atomic layer amidation technique
(2020-01-14)
Gu, Siyong
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Hsieh, Chien-Te
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Mallick, Bikash Chandra
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Gandomi, Yasser Ashraf
;
Chang, Jeng-Kuei
Nitrogen functionalization on graphene sheets has solely been demonstrated with a stepwise amidation implementation within the literature. The present work proposes an atomic layer amidation (ALN) technique to linearly adjust the surface amidation level on the carbon nanostructures. The ALN cycling protocol proposed in this work consists of an ammonia pulse, nitrogen pulse, and pumping at 100 and 150 degrees C. Both surface amidation and oxidation levels were linearly controlled by the ALN cycle number. The ALN technique was demonstrated as a self-limiting process capable of step-by-step N-functionalizing graphene oxide (GO) sheets on the atomic scale. The amidation reaction rates were ca. 0.023 (100 degrees C) and 0.028 atomic percent (at%) cycle(-1) (150 degrees C), and the apparent activation energy was determined to be 14.3 kJ mol(-1) (= 0.148 eV atom(-1)) from the Arrhenius equation. The amidation mechanism for forming the "chemical N" and "lattice N" at an atomic level was also proposed. Linearly controlling the optical band-gap with the ALN cycle number was suggested as a robust method for tuning the oxidation as well as the amidation level on the GO sheets. In this sense, nitrogen functionalization can be utilized for engineering any desirable properties within the graphene sheets.
Atomic layer oxidation on graphene sheets for tuning their oxidation levels, electrical conductivities, and band gaps
(2018-09-07)
Gu, Siyong
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Hsieh, Chien-Te
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Lin, Tzu-Wei
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Yuan, Chun-Yao
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Gandomi, Yasser Ashraf
Graphene sheets that can exhibit electrical conducting and semiconducting properties are highly desirable and have potential applications in fiber communications, photodetectors, solar cells, semiconductors, and broadband modulators. However, there is currently no efficient method that is able to tune the band gap of graphene sheets. This work adopts an efficient atomic layer oxidation (ALO) technique to cyclically increase the oxidation level of graphene sheets, thus, tuning their electrical conductance, band-gap structure, and photoluminescence (PL) response. The O/C atomic ratio as an increasing function of the ALO cycle number reflects two linear regions: 0.23% per cm(2) per cycle (0-15 cycles) and 0.054% per cm(2) per cycle (15-100 cycles). The excellent correlation coefficients reveal that the ALO process follows a self-limiting route to step-by-step oxidize graphene layers. The interlayer distance of ALO-graphene sheets shows an obvious increase after the ALO treatment, proved by X-ray diffraction. As analyzed by X-ray photon spectroscopy, the hydroxyl or epoxy group acts as a major contributor to the interlayer spacing distance and oxidation extent in the initial ALO stage, as compared to carbonyl and carboxyl groups. The ALO mechanism, based on Langmuir-Hinshelwood and Eley-Rideal models, is proposed to clarify the formation of oxygen functionalities and structural transformation from pristine graphene sheets to oxidized ones during the ALO cycle. With a tunable oxidation level, the electrical resistivity, semiconductor character, and PL response of ALO-graphene samples can be systematically controlled for desired applications. The ALO approach is capable of offering a straightforward route to tune the oxidation level of graphene sheets or other carbons.
Fluorescence of functionalized graphene quantum dots prepared from infrared-assisted pyrolysis of citric acid and urea
(2020-01-01)
Gu, Siyong
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Hsieh, Chien-Te
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Yuan, Chun-Yao
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Gandomi, Yasser Ashraf
;
Chang, Jeng-Kuei
This paper reports an efficient fabrication of N-doped graphene quantum dots (GQDs) showing controllable chemical and fluorescence (FL) properties through infrared carbonization (IRC) of citric acid and urea. The GQDs prefer to form an equilibrium shapes of circle with an average particle size ranged from 5 to 10 nm. The N/C atomic ratio in GQDs can be precisely tailored in a range from 21.6 to 49.6 at.% by simply controlling the weight ratio of citric acid to urea. With increasing the urea content, the GQDs not only contain N-doped graphene but also incorporate with crystalline cyanuric acid, forming a binary crystallinity. The quantum yield of 22.2% is achieved by N-doped GQDs, prepared from the IRC synthesis of chemical precursor at the citric acid/urea at 3:1. Excessive N and cyanuric acid can lead to FL quenching, red shift and wide spectral distribution. The design of GQDs possesses a multiple chromophoric band-gap structure, originated from the presence of cyanuric acid, defect-related emissive traps, and functional group distributions. This work offers an effective and inspiring approach to engineering both chemical compositions and unique crystalline structures of GQDs, and will therefore facilitate their fundamental research and applications to optical, sensing, energy and biological fields.
Highly concentrated carbonate electrolyte for Li-ion batteries with lithium metal and graphite anodes
(2020-02-29)
Xie, Jian-De
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Patra, Jagabandhu
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Rath, Purna Chandra
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Liu, Weng-Jing
;
Su, Ching-Yuan
Highly concentrated lithium bis(fluorosulfonyflimide (LiFSI) salt dissolved in carbonate solvent is employed as a high-performance and robust organic electrolyte for Li-ion batteries. The influences of Li salt type, concentration, and solvent type (such as diethyl carbonate (DEC), dimethyl carbonate (DMC), and ethylene carbonate (EC)) on the electrochemical properties of Li metal and graphite anodes are systematically assessed. A superior electrolyte composition of 5.5 M LiFSI-DMC/EC is achieved, enhancing the anti-flammability, coulombic efficiency, and high rate capability. The optimal efficiency values of Li electrodeposition/stripping utilizing 5.5 M LiFSI-DMC/EC are 97.0% and 94.5% at 0.4 and 6 mA cm(-2), respectively. Such an enhanced performance is due to the formation of a three-dimensional ion network, composed of contact ion pairs (CIPs) and ion aggregates (AGGs) in the highly concentrated LiFSI electrolyte, which effectively decreases the number of free solvent molecules and inhibits the formation of undesired dendritic Li structures. Raman spectroscopy is employed to confirm the formation of CIP and AGG compounds within the electrolyte. The electrochemical data of the 5.5 M LiFSI-DMC/EC electrolyte cell demonstrates a remarkable improvement in the specific capacity and rate capability of a graphite anode.
Hydrous ruthenium oxide-tantalum pentoxide thin film electrodes prepared by thermal decomposition for electrochemical capacitors
(2020-07-01)
Xie, Jian-De
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Hsu, Kai-Hsiang
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Patra, Jagabandhu
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Su, Ching-Yuan
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Lee, Sheng-Wei
In this work, we have fabricated high-performance thin-film electrodes for electrochemical capacitors (ECs) via thermal decomposition syntheses of RuO2-Ta2O5 coating layers on Ti substrates. The influences of decomposition temperature as well as the Ru/Ta molar ratio on material and electrochemical properties of the EC electrodes are systematically investigated. The thermal decomposition of 300 degrees C preserves a large fraction of hydrous RuO2 center dot xH(2)O within the hybrid oxide and consequently improves the electrode capacitance. The amorphous Ta2O5 incorporation can manipulate the RuO2 crystallinity and thus its specific capacitance. An optimal Ru/Ta molar ratio of 7:3 is determined for the RuO2-Ta2O5 electrode, which can deliver an energy density of 4.8 Wh kg(-1) at a power density of 8720 W kg(-1) (or 8.3 Wh L-1 at 15,000 W L-1). In addition, an excellent durability of 97.6% capacitance retention after 3000 charge-discharge cycles is found for this electrode. The proposed RuO2-Ta2O5 thin-film electrode has paved the way for next-generation ECs with superior capacitances, energy/power densities, and cyclability.
Improved lithium storage capacity and high rate capability of nitrogen-doped graphite-like electrode materials prepared from thermal pyrolysis of graphene quantum dots
(2020-09-10)
Gu, Siyong
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Christensen, Tommiejean
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Hsieh, Chien-Te
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Mallick, Bikash Chandra
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Gandomi, Yasser Ashraf
Adopting a solid-phase microwave-assisted technique followed by thermal pyrolysis of N-functionalized graphene quantum dots, novel nitrogen-doped graphite-like (NGL) electrode materials were synthesized and served as the anode for Li-ion batteries. The NGL anode demonstrated reversible capacity of 530 mAh g(-1) at 0.1C, superior rate capability at high C rate operation (420 mAh g(-1) at 5C), remarkable initial coulombic efficiency (>95.7%), and excellent cyclic stability along with high efficiency (>99.1%) during entire cycling. The NGL anode nanostructure enables improved lithium ion mobility and reversible Li+ storage during cycling. The analysis of the Ragone plots revealed that the specific energy of NGL anode reaches to ca. 840 Wh kg(-1) at the power density of 4200 W kg(-1). The diffusion coefficient of Li ions was measured as 1.69 x 10(-9) cm(2) s(-1) for the NGL anode material, substantially improving over commonly used graphite electrodes (15-26 times higher Li+ diffusivity). The high-rate cyclability as well as the cyclic stability of the NGL anodes were also confirmed via long-term cycling of full pouch cells assembled with ternary cathode and NGL anode. The robust design of the NGL anode materials introduced in this work, paves the way for designing next-generation lithium-ion batteries operating at ultrahigh C rates. (C) 2020 Elsevier Ltd. All rights reserved.
Ionic Liquids with Various Constituent Ions To Optimize Non-Enzymatic Electrochemical Detection Properties of Graphene Electrodes
(2019-10-07)
Xie, Jian-De
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Wang, Chueh-Han
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Patra, Jagabandhu
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Rath, Purna Chandra
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Gandomi, Yasser Ashraf
Palladium (Pd) nanoparticles, ionic liquids (ILs), or both are integrated with graphene sheets to serve as an electrochemical sensor for detecting various bio-species. Ascorbic acid (AA), uric acid (UA), and dopamine (DA) are used as the model analytes. To assess the effects of the constituent ions of ILs on sensing properties, various ILs, namely, EMI-SCN, EMI-DCA, BMP-DCA, BMI-PF6, EMI-NTF2, and BMP-NTF2, are investigated. The results demonstrate that the graphene/IL electrode shows superior detection sensitivity compared to those of the graphene/Pd and graphene/Pd/IL electrodes. Interestingly, the IL anions are found to play a crucial role in sensing performance. Angle-resolved X-ray photoelectron spectroscopy reveals that graphene can create an aligned cation/anion orientation in the adsorbed IL film, with the anions preferentially occupying the topmost surface, thus dominating the interaction with analytes. The graphene/EMI-SCN electrode shows the highest sensitivity among the electrodes, 1.49 mu A mu M-1 cm(-2), and a detection limit of 0.11 mu M toward DA. Even with large excesses of AA and UA, the concentration of DA can be effectively detected.
Microwave growth and tunable photoluminescence of nitrogen-doped graphene and carbon nitride quantum dots
(2019-05-14)
Gu, Siyong
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Hsieh, Chien-Te
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Gandomi, Yasser Ashraf
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Chang, Jeng-Kuei
;
Li, Ju
Tunable photoluminescent nitrogen-doped graphene and graphitic carbon nitride (g-C3N4) quantum dots are synthesized via a facile solid-phase microwave-assisted (SPMA) technique utilizing the pyrolysis of citric acid and urea precursors. The atomic ratio, surface functionalization, and atomic structure of as-prepared quantum dots strongly depend on the ratio of citric acid to urea. The quantum dots have a homogeneous particle size and tend to form a circle and/or ellipse shape to minimize the edge free energy. The atomic ratio of surface nitrogen to carbon (N/C) in the quantum dots can reach as high as 1.74, among the highest values reported in the literature. The SPMA technique is capable of producing high-quality quantum dots with photoluminescence (PL) emission at various wavelengths on a pilot scale. The atomic structures of the N-doped graphene and g-C3N4 quantum dots are explored using molecular dynamics simulations. Increasing the urea concentration increases the tendency of in-plane N (i.e., quaternary N) substitution over that of other amino functionalizations, such as pyrrolic and pyridinic N. The PL emission can be precisely tuned via a one-step SPMA method by adjusting the precursor composition. A high quantum yield of 38.7% is achieved with N-doped graphene quantum dots, indicating the substantial influence of the N- and O-rich edge groups on the enhancement of PL efficiency. A bandgap structure is proposed to describe the interstate (*-) transition of quantum dots. This work introduces a novel approach for engineering the chemical composition and atomic structure of graphene and g-C3N4 quantum dots, facilitating their research and applications in optical, electronic, and biomedical devices.
Prior vacuuming for supercritical fluid synthesis of SnO2/graphene nanocomposites with superior electrochemical Li+ storage performance
(2018-12-01)
Xie, Jian-De
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Li, Hui-Ying
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Umesh, Bharath
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Lee, Tai-Chou
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Chang, Jeng-Kuei
Supercritical CO2 (SCCO2) fluid, exhibiting gas-like diffusivity, extremely low viscosity, and near-zero surface tension, is used to synthesize uniformly dispersed and tightly anchored SO2 nanoparticles (a 3-nm diameter was achieved) on graphene nanosheets (GNSs). Usually, the conventional synthesis processes (in the absence of SCCO2) results in aggregated SnO2 clusters; whereas the technique described in this work eliminates this limitation. This study reveals the significance of two crucial factors (the SCCO2 pressure (i.e., fluid density) and the degassing step (i.e., vacuuming stage) in autoclave before injecting CO2) on the uniform distribution of the synthesized SnO2 nanoparticles on GNSs. Increasing the pressure leads to an increase in SCCO2 density (and viscosity), suppressing the transport of SnO2 precursors throughout the sample. On the other hand, vacuuming the autoclave before injecting CO2 improves the uniformity of SnO2 particle distributions. To assess the electrochemical performance of the synthesized nanoparticles, the specific capacity, rate capability, and cyclic stability were determined for various samples. A capacity of similar to 787 mAh g(-1) at 100 mA g(-1) was achieved for an optimal configuration of the SnO2/GNS electrodes. The capacity retention was 60% when the charge-discharge rate increased to 6000 mA g(-1). (C) 2018 Elsevier Ltd. All rights reserved.
Superior coulombic efficiency of lithium anodes for rechargeable batteries utilizing high-concentration ether electrolytes
(2019-10-01)
Xie, Jian-De
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Liu, Weng-Jing
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Li, Chi
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Patra, Jagabandhu
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Gandomi, Yasser Ashraf
This study adopts high-concentration ether electrolytes to improve high-rate capability, cycling stability, and Coulombic efficiency (CE) for lithium ion batteries with lithium anode. A series of ether-based electrolytes including lithium bis(fluorosulfonyl) imide (LiFSI)-glyme/ethylene carbonate (EC), LiFSI-glyme/EC, LiFSI-diglyme/EC, LiFSI-triglyme/EC, LiFSI-tetraglyme (G4)/EC, and LiFSI-1,3-dioxolane (DOL)/EC, along with commonly used LiPF6-DEC/EC were prepared to delineate the influences of concentration, chain length, molecular structure (linear or ring ether), and EC additive on the electrochemical performance of Li anodes. An optimum composition for ether-based electrolyte was determined resulting in significant improvement in anti-flammability as well as CE at both low and high rates. At ultra-high current density operation (e.g. 6 mA cm(-2)), the CE was 95.5 and 97.1% with 3 M LiFSI-G4/EC and 3 M LiFSI-DOL/EC, respectively. Using 1 M LiPF6 carbonate-based electrolyte tend to grow a needle-like dendritic structure when depositing lithium metal on Cu foils, whereas high-concentration ether electrolyte promotes a knot-like and rounded Li metal microstructure. High concentration EC-based electrolytes, are capable of facilitating Li thorn almost in tandem with solvent molecules, thereby reducing the number of free molecules, reducing the chance of side reaction with Li metal, and subsequently inhibiting the formation of dendritic Li structures. (C) 2019 Elsevier Ltd. All rights reserved.
Tailoring fluorescence emissions, quantum yields, and white light emitting from nitrogen-doped graphene and carbon nitride quantum dots
(2019-09-21)
Gu, Siyong
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Hsieh, Chien-Te
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Gandomi, Yasser Ashraf
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Li, Jianlin
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Yue, Xing Xing
Highly fluorescent N-doped graphene quantum dots (NGQDs) and graphitic carbon nitride quantum dots (CNQDs, g-C3N4) were synthesized using a solid-phase microwave-assisted (SPMA) technique. The SPMA method, based on the pyrolysis of citric acid and urea with different recipes, is capable of producing quantum dots with coexisting NGQDs and CNQDs at 280 degrees C within only five minutes. The photoluminescence (PL) emissions from NGQD and CNQDs are strongly dependent on the excitation wavelength and the solvent type, i.e., water, ethanol, and N-methyl pyrrolidinone. The unique attribute of the quantum dots, possessing a multiple chromophoric band-gap structure, originates from the presence of g-C3N4, defect-related emissive traps, and grain boundaries. Thus, an appropriate excitation wavelength induces a conjugated pi electron system to fulfill the most probable absorption band, resulting in wavelength-dependent emissions including ultraviolet, visible and infrared light. The quantum yield of the NGQD and CNQD samples can reach as high as 68.1%. Accordingly, a light-emitting device using the combination of the NGQD and CNQD powder embedded polymeric film can emit white-like light with ultra-high power-conversion efficiency.