Interface and Morphology Engineered Amorphous Si for Ultrafast Electrochemical Lithium Storage.

Ultrafast high-capacity lithium-ion batteries are extremely desirable for portable electronic devices, where Si is the most promising alternative to the conventional graphite anode due to its very high theoretical capacity. However, the low electronic conductivity and poor Li-diffusivity limit its rate capability. Moreover, high volume expansion/contraction upon Li-intake/uptake causes severe pulverization of the electrode, leading to drastic capacity fading. Here, interface and morphology-engineered amorphous Si matrix is being reported utilizing a few-layer vertical graphene (VG) buffer layer to retain high capacity at both slow and fast (dis)charging rates. The flexible mechanical support of VG due to the van-der-Waals interaction between the graphene layers, the weak adhesion between Si and graphene, and the highly porous geometry mitigated stress, while the three-dimensional mass loading enhanced specific capacity. Additionally, the high electronic conductivity of VG boosted rate-capability, resulting in a reversible gravimetric capacity of ≈1270 mAh g-1 (areal capacity of ≈37 µAh cm-2) even after 100 cycles at an ultrafast cycling rate of 20C, which provides a fascinating way for conductivity and stress management to obtain high-performance storage devices.

Electrostatic Gating of Monolayer Graphene by Concentrated Aqueous Electrolytes.

Electrostatic gating using electrolytes is a powerful approach for controlling the electronic properties of atomically thin two-dimensional materials such as graphene. However, the role of the ionic type, size, and concentration and the resulting gating efficiency is unclear due to the complex interplay of electrochemical processes and charge doping. Understanding these relationships facilitates the successful design of electrolyte gates and supercapacitors. To that end, we employ in situ Raman microspectroscopy combined with electrostatic gating using various concentrated aqueous electrolytes. We show that while the ionic type and concentration alter the initial doping state of graphene, they have no measurable influence over the rate of the doping of graphene with applied voltage in the high ionic strength limit of 3-15 M. Crucially, unlike for conventional dielectric gates, a large proportion of the applied voltage contributes to the Fermi level shift of graphene in concentrated electrolytes. We provide a practical overview of the doping efficiency for different gating systems.

Isotope Engineered Fluorinated Single and Bilayer Graphene: Insights into Fluorination Selectivity, Stability, and Defect Passivation.

Tailoring the physicochemical properties of graphene through functionalization remains a major interest for next-generation technological applications. However, defect formation due to functionalization greatly endangers the intrinsic properties of graphene, which remains a serious concern. Despite numerous attempts to address this issue, a comprehensive analysis has not been conducted. This work reports a two-step fluorination process to stabilize the fluorinated graphene and obtain control over the fluorination-induced defects in graphene layers. The structural, electronic and isotope-mass-sensitive spectroscopic characterization unveils several not-yet-resolved facts, such as fluorination sites and CF bond stability in partially-fluorinated graphene (F-SLG). The stability of fluorine has been correlated to fluorine co-shared between two graphene layers in fluorinated-bilayer-graphene (F-BLG). The desorption energy of co-shared fluorine is an order of magnitude higher than the CF bond energy in F-SLG due to the electrostatic interaction and the inhibition of defluorination in the F-BLG. Additionally, F-BLG exhibits enhanced light-matter interaction, which has been utilized to design a proof-of-concept field-effect phototransistor that produces high photocurrent response at a time <200 µs. Thus, the study paves a new avenue for the in-depth understanding and practical utilization of fluorinated graphenic carbon.

Electrical Contact Resistance of Large-Area Graphene on Pre-Patterned Cu and Au Electrodes.

Contact resistance between electrically connected parts of electronic elements can negatively affect their resulting properties and parameters. The contact resistance is influenced by the physicochemical properties of the connected elements and, in most cases, the lowest possible value is required. The issue of contact resistance is also addressed in connection with the increasingly frequently used carbon allotropes. This work aimed to determine the factors that influence contact resistance between graphene prepared by chemical vapour deposition and pre-patterned Cu and Au electrodes onto which graphene is subsequently transferred. It was found that electrode surface treatment methods affect the resistance between Cu and graphene, where contact resistance varied greatly, with an average of 1.25 ± 1.54 kΩ, whereas for the Au electrodes, the deposition techniques did not influence the resulting contact resistance, which decreased by almost two orders of magnitude compared with the Cu electrodes, to 0.03 ± 0.01 kΩ.

The Effects of Ultrasound Treatment of Graphite on the Reversibility of the (De)Intercalation of an Anion from Aqueous Electrolyte Solution.

Low cycling stability is one of the most crucial issues in rechargeable batteries. Herein, we study the effects of a simple ultrasound treatment of graphite for the reversible (de)intercalation of a ClO4- anion from a 2.4 M Al(ClO4)3 aqueous solution. We demonstrate that the ultrasound-treated graphite offers the improved reversibility of the ClO4- anion (de)intercalation compared with the untreated samples. The ex situ and in situ Raman spectroelectrochemistry and X-ray diffraction analysis of the ultrasound-treated materials shows no change in the interlayer spacing, a mild increase in the stacking order, and a large increase in the amount of defects in the lattice accompanied by a decrease in the lateral crystallite size. The smaller flakes of the ultrasonicated natural graphite facilitate the improved reversibility of the ClO4- anion electrochemical (de)intercalation and a more stable electrochemical performance with a cycle life of over 300 cycles.

Enhanced and Faster Potassium Storage in Graphene with Respect to Graphite: A Comparative Study with Lithium Storage.

The mechanisms, extent, and rate of K-storage in graphenic and graphitic carbons, as direct comparisons with Li-storage in the same structures/materials, in terms of the effects of dimensional scale and presence of surface and exposed edge sites have been brought to the fore via DFT-based simulations, duly complemented and supplemented by experimental studies. The simulation indicates feasibilities toward K-storage on single-layer graphene (SLG) at a concentration greater than that in graphite ( i. e., beyond KC8), the formation of more than one layer of K on SLG, and K-storage on both the surfaces of SLG, unlike that for Li-storage. Simulations done with graphene nanoribbons (GNRs) indicate that K can get hosted on the graphene surfaces and at the exposed "stepped" edges, in addition to the "classical" K-intercalation in-between the constituent graphene layers. Accordingly, the computation studies indicate considerably enhanced K-storage "specific capacity" of GNR, as compared to bulk graphite, with the capacity decreasing with the increase in number of graphene layers. Electrochemical potassiation/depotassiation of well-ordered fairly pristine few layers graphene films (FLG; ∼6-7 layers) confirms the simultaneous occurrences of bulk ( i. e., K-intercalation) and surface storage of K, resulting in reversible K-storage capacity being greater than that of thicker bulk graphite films by a factor of ∼2.5. This is in agreement with the predictions from DFT. However, this increment is less compared to that for Li-storage, again in accordance with the DFT results. Our measurements indicate lower diffusivity of K, as compared to Li, in the same graphitic structure by an order of magnitude. Accordingly, the rate capability of K-storage in graphite has been found to be considerably inferior to Li-storage, which renders the reduction in dimensional scale even more important in the case of K-storage, as observed here with FLG.

Correlations between preparation methods, structural features and electrochemical Li-storage behavior of reduced graphene oxide.

Wide differences in the structural features of graphenic carbon, especially in the case of reduced graphene oxides (rGO), are expected to have considerable impacts on the properties, thus leading to significant scatter and poor understanding/prediction of their performances for various applications, including as electrode materials for electrochemical Li-storage. In this context, the present work develops a comprehensive understanding (via thorough experimentation, including in situ X-ray diffraction studies, and analysis) on the effects of graphene oxide (GO) reduction methods/conditions on the structural features (mainly 'graphenic' ordering) and concomitant influences of the same on electrochemical Li-storage behavior. 'Moderately oxidized' GO (O/C ∼0.41) was reduced via three different methods, viz., (i) using hydrazine hydrate vapor at room temperature (rGO-H; O/C ∼0.23), (ii) thermal reduction by annealing at just 500 °C (rGO-A; O/C ∼0.20) and (iii) hydrazine treatment, followed by the same annealing treatment (rGO-HA; O/C ∼0.17). Raman spectroscopy, in situ X-ray diffraction recorded during annealing and high resolution TEM imaging indicate that while GO and rGO-H had considerable defect contents [I(D)/I(G) ∼1.4 for rGO-H], including a very non-uniform interlayer spacing (varying between 3.1 and 3.6 Å), the 500 °C annealed rGO-A and rGO-HA had significantly reduced defect contents [I(D)/I(G) ∼0.6] and near-perfect 'graphenic' ordering with a uniform interlayer spacing of ∼3.35 Å. Despite the nanoscaled dimensions, defect structures, especially the non-uniform interlayer spacing, resulted in relatively poor reversible Li-capacity and rate capability for the non-annealed rGO-H, even in comparison to the bulk graphitic carbon. By contrast, the annealed rGOs, especially the rGO-HA, not only possessed a superior reversible Li-capacity of ∼450 mA h g-1 (at C/20), but also exhibited a significantly improved rate capability (even compared to most rGOs reported in the literature), retaining ∼120 mA h g-1 along with flat potential profile (below ∼0.2 V against Li/Li+) even at 10C (as possibly never reported before with graphitic/graphenic carbons).