Zhaoyang Lin

Flexible Solid-State Supercapacitors Based on Three-Dimensional Graphene Hydrogel Films

Flexible solid-state supercapacitors are of considerable interest as mobile power supply for future flexible electronics. Graphene or carbon nanotubes based thin films have been used to fabricate flexible solid-state supercapacitors with high gravimetric specific capacitances (80-200 F/g), but usually with a rather low overall or areal specific capacitance (3-50 mF/cm(2)) due to the ultrasmall electrode thickness (typically a few micrometers) and ultralow mass loading, which is not desirable for practical applications. Here we report the exploration of a three-dimensional (3D) graphene hydrogel for the fabrication of high-performance solid-state flexible supercapacitors. With a highly interconnected 3D network structure, graphene hydrogel exhibits exceptional electrical conductivity and mechanical robustness to make it an excellent material for flexible energy storage devices. Our studies demonstrate that flexible supercapacitors with a 120 μm thick graphene hydrogel thin film can exhibit excellent capacitive characteristics, including a high gravimetric specific capacitance of 186 F/g (up to 196 F/g for a 42 μm thick electrode), an unprecedented areal specific capacitance of 372 mF/cm(2) (up to 402 mF/cm(2) for a 185 μm thick electrode), low leakage current (10.6 μA), excellent cycling stability, and extraordinary mechanical flexibility. This study demonstrates the exciting potential of 3D graphene macrostructures for high-performance flexible energy storage devices.

High-performance transition metal–doped Pt3Ni octahedra for oxygen reduction reaction

Molybdenum doping drives high activity Platinum (Pt) is an effective catalyst of the oxygen reduction reaction in fuel cells but is scarce. One approach to extend Pt availability is to alloy it with more abundant metals such as nickel (Ni). Although these catalysts can be highly active, they are often not durable because of Ni loss. Huang et al. show that doping the surface of octahedral Pt3Ni nanocrystals with molybdenum not only leads to high activity (∼80 times that of a commercial catalyst) but enhances their stability. Science, this issue p. 1230 Molybdenum-doped platinum-nickel nanocrystal catalysts exhibit high activity and durability for a key fuel cell reaction. Bimetallic platinum-nickel (Pt-Ni) nanostructures represent an emerging class of electrocatalysts for oxygen reduction reaction (ORR) in fuel cells, but practical applications have been limited by catalytic activity and durability. We surface-doped Pt3Ni octahedra supported on carbon with transition metals, termed M‐Pt3Ni/C, where M is vanadium, chromium, manganese, iron, cobalt, molybdenum (Mo), tungsten, or rhenium. The Mo‐Pt3Ni/C showed the best ORR performance, with a specific activity of 10.3 mA/cm2 and mass activity of 6.98 A/mgPt, which are 81- and 73‐fold enhancements compared with the commercial Pt/C catalyst (0.127 mA/cm2 and 0.096 A/mgPt). Theoretical calculations suggest that Mo prefers subsurface positions near the particle edges in vacuum and surface vertex/edge sites in oxidizing conditions, where it enhances both the performance and the stability of the Pt3Ni catalyst.

Holey graphene frameworks for highly efficient capacitive energy storage

Supercapacitors represent an important strategy for electrochemical energy storage, but are usually limited by relatively low energy density. Here we report a three-dimensional holey graphene framework with a hierarchical porous structure as a high-performance binder-free supercapacitor electrode. With large ion-accessible surface area, efficient electron and ion transport pathways as well as a high packing density, the holey graphene framework electrode can deliver a gravimetric capacitance of 298 F g(-1) and a volumetric capacitance of 212 F cm(-3) in organic electrolyte. Furthermore, we show that a fully packaged device stack can deliver gravimetric and volumetric energy densities of 35 Wh kg(-1) and 49 Wh l(-1), respectively, approaching those of lead acid batteries. The achievement of such high energy density bridges the gap between traditional supercapacitors and batteries, and can open up exciting opportunities for mobile power supply in diverse applications.

Functionalized Graphene Hydrogel‐Based High‐Performance Supercapacitors

Functionalized graphene hydrogels are prepared by a one-step low-temperature reduction process and exhibit ultrahigh specific capacitances and excellent cycling stability in the aqueous electrolyte. Flexible solid-state supercapacitors based on functionalized graphene hydrogels are demonstrated with superior capacitive performances and extraordinary mechanical flexibility.

Ultrafine jagged platinum nanowires enable ultrahigh mass activity for the oxygen reduction reaction

An activity lift for platinum Platinum is an excellent but expensive catalyst for the oxygen reduction reaction (ORR), which is critical for fuel cells. Alloying platinum with other metals can create shells of platinum on cores of less expensive metals, which increases its surface exposure, and compressive strain in the layer can also boost its activity (see the Perspective by Stephens et al.). Bu et al. produced nanoplates—platinum-lead cores covered with platinum shells—that were in tensile strain. These nanoplates had high and stable ORR activity, which theory suggests arises from the strain optimizing the platinum-oxygen bond strength. Li et al. optimized both the amount of surface-exposed platinum and the specific activity. They made nanowires with a nickel oxide core and a platinum shell, annealed them to the metal alloy, and then leached out the nickel to form a rough surface. The mass activity was about double the best reported values from previous studies. Science, this issue p. 1410, p. 1414; see also p. 1378 Improving the platinum (Pt) mass activity for the oxygen reduction reaction (ORR) requires optimization of both the specific activity and the electrochemically active surface area (ECSA). We found that solution-synthesized Pt/NiO core/shell nanowires can be converted into PtNi alloy nanowires through a thermal annealing process and then transformed into jagged Pt nanowires via electrochemical dealloying. The jagged nanowires exhibit an ECSA of 118 square meters per gram of Pt and a specific activity of 11.5 milliamperes per square centimeter for ORR (at 0.9 volts versus reversible hydrogen electrode), yielding a mass activity of 13.6 amperes per milligram of Pt, nearly double previously reported best values. Reactive molecular dynamics simulations suggest that highly stressed, undercoordinated rhombus-rich surface configurations of the jagged nanowires enhance ORR activity versus more relaxed surfaces.

A Facile Strategy to Pt3Ni Nanocrystals with Highly Porous Features as an Enhanced Oxygen Reduction Reaction Catalyst

A facile strategy to Pt3Ni nanocrystals with highly porous features is developed. The integration of a high surface area and rich step/edge atoms endows the nanocrystals with an impressive oxygen reduction reaction (ORR) specific activity and mass activity. These nanocrystals are more stable in ORR and show a small activity change after 6000 potential sweeps. This is a promising material for practical electrocatalytic applications.

Solution Processable Holey Graphene Oxide and Its Derived Macrostructures for High-Performance Supercapacitors

Scalable preparation of solution processable graphene and its bulk materials with high specific surface areas and designed porosities is essential for many practical applications. Herein, we report a scalable approach to produce aqueous dispersions of holey graphene oxide with abundant in-plane nanopores via a convenient mild defect-etching reaction and demonstrate that the holey graphene oxide can function as a versatile building block for the assembly of macrostructures including holey graphene hydrogels with a three-dimensional hierarchical porosity and holey graphene papers with a compact but porous layered structure. These holey graphene macrostructures exhibit significantly improved specific surface area and ion diffusion rate compared to the nonholey counterparts and can be directly used as binder-free supercapacitor electrodes with ultrahigh specific capacitances of 283 F/g and 234 F/cm(3), excellent rate capabilities, and superior cycling stabilities. Our study defines a scalable pathway to solution processable holey graphene materials and will greatly impact the applications of graphene in diverse technological areas.

One-step strategy to graphene/Ni(OH)2 composite hydrogels as advanced three-dimensional supercapacitor electrode materials

AbstractGraphene-based three-dimensional (3D) macroscopic materials have recently attracted increasing interest by virtue of their exciting potential in electrochemical energy conversion and storage. Here we report a facile one-step strategy to prepare mechanically strong and electrically conductive graphene/Ni(OH)2 composite hydrogels with an interconnected porous network. The composite hydrogels were directly used as 3D supercapacitor electrode materials without adding any other binder or conductive additives. An optimized composite hydrogel containing ∼82 wt.% Ni(OH)2 exhibited a specific capacitance of ∼1,247 F/g at a scan rate of 5 mV/s and ∼785 F/g at 40 mV/s (∼63% capacitance retention) with excellent cycling stability. The capacity of the 3D hydrogels greatly surpasses that of a physical mixture of graphene sheets and Ni(OH)2 nanoplates (∼309 F/g at 40 mV/s). The same strategy was also applied to fabricate graphene-carbon nanotube/Ni(OH)2 ternary composite hydrogels with further improved specific capacitances (∼1,352 F/g at 5 mV/s) and rate capability (∼66% capacitance retention at 40 mV/s). Both composite hydrogels obtained here can deliver high energy densities (∼43 and ∼47 Wh/kg, respectively) and power densities (∼8 and ∼9 kW/kg, respectively), making them attractive electrode materials for supercapacitor applications. This study opens a new pathway to the design and fabrication of functional 3D graphene composite materials, and can significantly impact broad areas including energy storage and beyond.

Large Area Growth and Electrical Properties of p-Type WSe2 Atomic Layers

Transition metal dichacogenides represent a unique class of two-dimensional layered materials that can be exfoliated into single or few atomic layers. Tungsten diselenide (WSe2) is one typical example with p-type semiconductor characteristics. Bulk WSe2 has an indirect band gap (∼1.2 eV), which transits into a direct band gap (∼1.65 eV) in monolayers. Monolayer WSe2, therefore, is of considerable interest as a new electronic material for functional electronics and optoelectronics. However, the controllable synthesis of large-area WSe2 atomic layers remains a challenge. The studies on WSe2 are largely limited by relatively small lateral size of exfoliated flakes and poor yield, which has significantly restricted the large-scale applications of the WSe2 atomic layers. Here, we report a systematic study of chemical vapor deposition approach for large area growth of atomically thin WSe2 film with the lateral dimensions up to ∼1 cm2. Microphotoluminescence mapping indicates distinct layer dependent efficiency. The monolayer area exhibits much stronger light emission than bilayer or multilayers, consistent with the expected transition to direct band gap in the monolayer limit. The transmission electron microscopy studies demonstrate excellent crystalline quality of the atomically thin WSe2. Electrical transport studies further show that the p-type WSe2 field-effect transistors exhibit excellent electronic characteristics with effective hole carrier mobility up to 100 cm2 V–1 s–1 for monolayer and up to 350 cm2 V–1 s–1 for few-layer materials at room temperature, comparable or well above that of previously reported mobility values for the synthetic WSe2 and comparable to the best exfoliated materials.

A rational design of cosolvent exfoliation of layered materials by directly probing liquid–solid interaction

Exfoliation of layered materials such as graphite and transition metal dichalcogenides into mono- or few-layers is of significant interest for both the fundamental studies and potential applications. Here we report a systematic investigation of the fundamental factors governing the liquid exfoliation process and the rational design of a cosolvent approach for the exfoliation of layered materials. We show that Youngs equation can be used to predict the optimal cosolvent concentration for the effective exfoliation of graphite and molybdenum disulphide in water mixtures with methanol, ethanol, isopropanol and t-butyl alcohol. Moreover, we find that the cosolvent molecular size has an important role in the exfoliation yield, attributed to the larger steric repulsion provided by the larger cosolvent molecules. Our study provides critical insight into the exfoliation of layered materials, and defines a rational strategy for the design of an environmentally friendly pathway to the high yield exfoliation of layered materials.