p–n Heterojunction of Doped Graphene Films Obtained by Pyrolysis of Biomass Precursors

Nitrogen‐doped graphene [(N)G] obtained by pyrolysis at 900 °C of nanometric chitosan films exhibits a Hall effect characteristic of n‐type semiconductors. In contrast, boron‐doped graphene [(B)G] obtained by pyrolysis of borate ester of alginate behaves as a p‐type semiconductor based also on the Hall effect. A p–n heterojunction of (B)G‐(N)G films is built by stepwise coating of a quartz plate using a mask. The heterojunction is created by the partial overlapping of the (B)G‐(N)G films. Upon irradiation with a xenon lamp of aqueous solutions of H₂PtCl₆ and MnCl₂ in contact with the heterojunction, preferential electron migration from (B)G to (N)G with preferential location of positive holes on (B)G is established by observation in scanning electron microscopy of the formation of Pt nanoparticles (NP) on (N)G and MnO₂ NP on (B)G. The benefits of the heterojunction with respect to the devices having one individual component as a consequence of the electron migration through the p‐n heterojunction are illustrated by measuring the photocurrent in the (B)G‐(N)G heterojunction (180% current enhancement with respect to the dark current) and compared it to the photocurrent of the individual (B)G (15% enhancement) and (N)G (55% enhancement) components.     

Ultrahigh Thermal Conductive yet Superflexible Graphene Films

Electrical devices generate heat at work. The heat should be transferred away immediately by a thermal manager to keep proper functions, especially for high‐frequency apparatuses. Besides high thermal conductivity (K ), the thermal manager material requires good foldability for the next generation flexible electronics. Unfortunately, metals have satisfactory ductility but inferior K (≤429 W m^?1 K^?1), and highly thermal‐conductive nonmetallic materials are generally brittle. Therefore, fabricating a foldable macroscopic material with a prominent K is still under challenge. This study solves the problem by folding atomic thin graphene into microfolds. The debris‐free giant graphene sheets endow graphene film (GF) with a high K of 1940 ± 113 W m^?1 K^?1. Simultaneously, the microfolds render GF superflexible with a high fracture elongation up to 16%, enabling it more than 6000 cycles of ultimate folding. The large‐area multifunctional GFs can be easily integrated into high‐power flexible devices for highly efficient thermal management.     

Critical Insight into the Relentless Progression Toward Graphene and Graphene‐Containing Materials for Lithium‐Ion Battery Anodes

Used as a bare active material or component in hybrids, graphene has been the subject of numerous studies in recent years. Indeed, from the first report that appeared in late July 2008, almost 1600 papers were published as of the end 2015 that investigated the properties of graphene as an anode material for lithium‐ion batteries. Although an impressive amount of data has been collected, a real advance in the field still seems to be missing. In this framework, attention is focused on the most prominent research efforts in this field with the aim of identifying the causes of such relentless progression through an insightful and critical evaluation of the lithium‐ion storage performances (i.e., 1^st cycle irreversible capacity, specific gravimetric and volumetric capacities, average delithiation voltage profile, rate capability and stability upon cycling). The “graphene fever” has certainly provided a number of fundamental studies unveiling the electrochemical properties of this “wonder” material. However, analysis of the published literature also highlights a loss of focus from the final application. Hype‐driven claims, not fully appropriate metrics, and negligence of key parameters are probably some of the factors still hindering the application of graphene in commercial batteries.     

Recent Progress in Graphene‐Based Noble‐Metal Nanocomposites for Electrocatalytic Applications

The fast industrialization process has led to global challenges in the energy crisis and environmental pollution, which might be solved with clean and renewable energy. Highly efficient electrochemical systems for clean‐energy collection require high‐performance electrocatalysts, including Au, Pt, Pd, Ru, etc. Graphene, a single‐layer 2D carbon nanosheet, possesses many intriguing properties, and has attracted tremendous research attention. Specifically, graphene and graphene derivatives have been utilized as templates for the synthesis of various noble‐metal nanocomposites, showing excellent performance in electrocatalytic‐energy‐conversion applications, such as the hydrogen evolution reaction and CO₂ reduction. Herein, the recent progress in graphene‐based noble‐metal nanocomposites is summarized, focusing on their synthetic methods and electrocatalytic applications. Furthermore, some personal insights on the challenges and possible future work in this research field are proposed.     

1‐Aza‐15‐Crown‐5 Functionalized Graphene Oxide for 2D Graphene‐Based Li+‐ion Conductor

Attachment of Li⁺ ion on graphene surface to realize Li⁺‐ion conductor is a real challenge because of the weak interaction between the ions and the functional groups of graphene oxide; although, a large number of theoretical results are already available in the literature. To overcome this problem, graphene oxide is functionalized by 1‐aza‐15‐crown‐5, the cage‐like structure containing four oxygens that can bind Li⁺ ion through electrostatic interaction. Li⁺ migration on graphene surface has been investigated using ac relaxation mechanism. Perfect Debye‐type relaxation behavior with β (relaxation exponent) value ≈1 resulting from single ion is observed. The activation energy of Li⁺ migration arising due to cation‐π interaction is found to be 0.37 eV, which agrees well with recently reported theoretical value. It is believed that this study will help to design isolated ion conductors for Li⁺‐ion battery.     

Enhanced Peltier Effect in Wrinkled Graphene Constriction by Nano‐Bubble Engineering

Inspired by the promising applications in thermopower generation from waste heat and active on‐chip cooling, the thermoelectric and electrothermal properties of graphene have been extensively pursued by seeking ingeniously designed structures with thermoelectric conversion capability. The graphene wrinkle is a ubiquitous structure formed inevitably during the synthesis of large‐scale graphene films but the corresponding properties for thermoelectric and electrothermal applications are rarely investigated. Here, the electrothermal Peltier effect from the graphene wrinkle fabricated on a germanium substrate is reported. Peltier cooling and heating across the wrinkle are visualized unambiguously with polarities consistent with p‐type doping and in accordance with the wrinkle spatial distribution. By direct patterning of the nano‐bubble structure, the current density across the wrinkle can be boosted by current crowding to enhance the Peltier effect. The observed Peltier effect can be attributed to the nonequilibrium charge transport by interlayer tunneling across the van der Waals barrier of the graphene wrinkle. The graphene wrinkle in combination with nano‐bubble engineering constitutes an innovative and agile platform to design graphene and other more general two‐dimensional (2D) thermoelectrics and opens the possibility for realizing active on‐chip cooling for 2D nanoelectronics with van der Waals junctions.     

Switching Vertical to Horizontal Graphene Growth Using Faraday Cage‐Assisted PECVD Approach for High‐Performance Transparent Heating Device

Plasma‐enhanced chemical vapor deposition (PECVD) is an applicable route to achieve low‐temperature growth of graphene, typically shaped like vertical nanowalls. However, for transparent electronic applications, the rich exposed edges and high specific surface area of vertical graphene (VG) nanowalls can enhance the carrier scattering and light absorption, resulting in high sheet resistance and low transmittance. Thus, the synthesis of laid‐down graphene (LG) is imperative. Here, a Faraday cage is designed to switch graphene growth in PECVD from the vertical to the horizontal direction by weakening ion bombardment and shielding electric field. Consequently, laid‐down graphene is synthesized on low‐softening‐point soda‐lime glass (6 cm × 10 cm) at ≈580 °C. This is hardly realized through the conventional PECVD or the thermal chemical vapor deposition methods with the necessity of high growth temperature (1000 °C–1600 °C). Laid‐down graphene glass has higher transparency, lower sheet resistance, and much improved macroscopic uniformity when compare to its vertical graphene counterpart and it performs better in transparent heating devices. This will inspire the next‐generation applications in low‐cost transparent electronics.