Femtosecond laser irradiation as a novel method for nanosheet growth and defect generation in g-C3N4.

Among the many recently developed photo-catalytic materials, graphitic carbon nitride (g-C3N4) shows great promise as a catalytic material for water splitting, hydrogen generation, and related catalytic applications. Herein, synthesized bulk g-C3N4is simply irradiated under a 35 fs pulse at mixed photon energies (800 nm and its second harmonic). g-C3N4was synthesized from melamine following a facile thermal polymerization procedure. The prepared material was introduced, in an aqueous environment, to the femtosecond laser for various lengths of time. The treated material demonstrates a significant increase in surface area, relative to the untreated samples, indicating that irradiation is a successful method for exfoliation. The subsequent characterization reveals that the mixed irradiation process drives significant defect generation and sheet growth, which is not seen under 800 nm irradiation. Extended mixed irradiation results in 4 nm thick nanosheets with lateral dimensions 4× that of the bulk material. The treated material shows improved dye absorption/removal. This novel method of defect generation and nanosheet growth shows great potential as a g-C3N4pre-treatment method for co-catalytic applications. Herein it is shown that femtosecond laser irradiation drives exfoliation beyond 100 nm particle sizes, and sheet-like morphologies under extended irradiation, which must be taken into account when using this method to improve material performance.

Salt-Induced Doping and Templating of Laser-Induced Graphene Supercapacitors.

The use of inexpensive and widely available CO2 lasers to selectively irradiate polymer films and form a graphene foam, termed laser-induced graphene (LIG), has incited significant research attention. The simple and rapid nature of the approach and the high conductivity and porosity of LIG have motivated its widespread application in electrochemical energy storage devices such as batteries and supercapacitors. However, nearly all high-performance LIG-based supercapacitors reported to date are prepared from costly, petroleum-based polyimide (Kapton, PI). Herein, we demonstrate that incorporating microparticles of inexpensive, non-toxic, and widely abundant sodium salts such as NaCl and Na2SO4 into poly(furfuryl alcohol) (PFA) resins enables the formation of high-performance LIG. The embedded particles aid in carbonization and act as a template for pore formation. While increasing both the carbon yield and surface area of the electrodes, the salt also dopes the LIG formed with S or Cl. The combination of these effects results in a two- to four-order-of-magnitude increase in device areal capacitance, from 8 µF/cm2 for PFA/no salt at 5 mV/s to up to 80 mF/cm2 for some PFA/20% Na2SO4 samples at 0.05 mA/cm2, significantly higher than that of PI-based devices and most other LIG precursors.

Encapsulating a Responsive Hydrogel Core for Void Space Modulation in High-Stability Graphene-Wrapped Silicon Anodes.

Due to its formidably high theoretical capacity (3590 mAh/g at room temperature), silicon (Si) is expected to replace graphite as the dominant anode for higher energy density lithium (Li)-ion batteries. However, stability issues stemming from silicon's significant volume expansion (∼300%) upon lithiation have slowed down commercialization. Herein, we report the design of a scalable process to engineer core-shell structures capable of buffering this volume expansion, which utilize a core made up of a poly(ethylene oxide)-carboxymethyl cellulose hydrogel and silicon protected by a crumpled graphene shell. The volume expansion of the hydrogel upon exposure to water creates a void space between the Si-Si and Si-rGO interfaces within the core when the gel dries. Unlike sacrificial spacers, the dehydrated hydrogel remains in the core and acts as an elastic Li-ion conductor, which improves the stability and high rate performance. The optimized composite electrodes retain ∼81.7% of their initial capacity (1055 mAh/(grGO+gel+Si)) after 320 cycles when an active material loading of 1 mg/cm2 is used. At more practical mass loadings (2.5 mg/cm2), the electrodes achieve 2.04 mAh/cm2 and retain 79% of this capacity after 200 cycles against a lithium half-cell. Full cells assembled using a lithium ion phosphate cathode lose only 6.7% of their initial capacity over 100 cycles, demonstrating the potential of this nanocomposite anode for use in next-generation Li-ion batteries.

Controlling Void Space in Crumpled Graphene-Encapsulated Silicon Anodes using Sacrificial Polystyrene Nanoparticles.

Silicon anodes have a theoretical capacity of 3590 mAh g-1 (for Li15 Si4 , at room temperature), which is tenfold higher than the graphite anodes used in current Li-ion batteries. This, and silicon's natural abundance, makes it one of the most promising materials for next-generation batteries. Encapsulating silicon nanoparticles (Si NPs) in a crumpled graphene shell by spray drying or spray pyrolysis are promising and scalable methods to produce core-shell structures, which buffer the extreme volume change (>300 vol %) caused by (de)lithiaton of silicon. However, capillary forces cause the graphene-based materials to tightly wrap around Si NP clusters, and there is little control over the void space required to further improve cycle life. Herein, a simple strategy is developed to engineer void-space within the core by incorporating varying amounts of similarly sized polystyrene (PS) nanospheres in the spray drier feed mixture. The PS completely decomposes during thermal reduction of the graphene oxide shell and results in Si cores of varying porosity. The best performance is achieved at a 1 : 1 ratio (PS/Si), leading to high capacities of 1638, 1468, and 1179 mAh g-1 Si+rGO at 0.1, 1, and 4 A g-1 , respectively. Moreover, at 1 A g-1 , the capacity retention is 80.6 % after 200 cycles. At a practical active material loading of 2.4 mg cm-2 , the electrodes achieve an areal capacity of 2.26 mAh cm-2 at 1 A g-1 .

Polymer Binders: Characterization and Development toward Aqueous Electrode Fabrication for Sustainability.

Binders play an important role in electrode processing for energy storage systems. While conventional binders often require hazardous and costly organic solvents, there has been increasing development toward greener and less expensive binders, with a focus on those that can be processed in aqueous conditions. Due to their functional groups, many of these aqueous binders offer further beneficial properties, such as higher adhesion to withstand the large volume changes of several high-capacity electrode materials. In this review, we first discuss the roles of binders in the construction of electrodes, particularly for energy storage systems, summarize typical binder characterization techniques, and then highlight the recent advances on aqueous binder systems, aiming to provide a stepping stone for the development of polymer binders with better sustainability and improved functionalities.

Nanoscale assembling of graphene oxide with electrophoretic deposition leads to superior percolation network in Li-ion electrodes: TiNb2O7/rGO composite anodes.

In this paper, electrophoretic deposition (EPD) is shown to promote nanoscale assembling of graphene oxide (GO) enabling the fabrication of highly homogeneous, robust, and capacity fade resistant composite titanium niobate (TiNb2O7, TNO)/rGO anodes upon reductive annealing. Control tests revealed that EPD is superior to conventional PVDF-based casting in maximizing the performance benefits from using reduced GO in Li-ion electrode fabrication as is the case of TNO that is plagued with conductivity and capacity fading problems. In this particular study, we show that there is a synergy developed between GO and EPD with the former (1) stabilizing the EPD suspension, (2) acting as a flexible binder net that affords mechanical integrity during the volume expansion of TNO, (3) serving as a conductive filler, and (4) contributing to Li-ion storage via pseudocapacitance. As a consequence, a superior percolation network is developed. Thus while both EPD- and PVDF- built TNO/rGO composite anodes exhibited high initial capacities (∼350 and 318 mA h g-1) at 0.5 C cycling, respectively, their cycling behaviour was quite different with the latter experiencing high internal polarization and extended degradation. Post-mortem PEEM-XANES analysis clearly demonstrated a highly homogeneous mesostructure in the case of the EPD-built TNO/rGO anode vs. a highly segregated and dis-jointed rGO and TNO component clustering in the PVDF-built electrode.