Surface chemistry and structure manipulation of graphene-related materials to address the challenges of electrochemical energy storage.

Energy storage devices are important components in portable electronics, electric vehicles, and the electrical distribution grid. Batteries and supercapacitors have achieved great success as the spearhead of electrochemical energy storage devices, but need to be further developed in order to meet the ever-increasing energy demands, especially attaining higher power and energy density, and longer cycling life. Rational design of electrode materials plays a critical role in developing energy storage systems with higher performance. Graphene, the well-known 2D allotrope of carbon, with a unique structure and excellent properties has been considered a "magic" material with its high energy storage capability, which can not only aid in addressing the issues of the state-of-the-art lithium-ion batteries and supercapacitors, but also be crucial in the so-called post Li-ion battery era covering different technologies, e.g., sodium ion batteries, lithium-sulfur batteries, structural batteries, and hybrid supercapacitors. In this feature article, we provide a comprehensive overview of the strategies developed in our research to create graphene-based composite electrodes with better ionic conductivity, electron mobility, specific surface area, mechanical properties, and device performance than state-of-the-art electrodes. We summarize the strategies of structure manipulation and surface modification with specific focus on tackling the existing challenges in electrodes for batteries and supercapacitors by exploiting the unique properties of graphene-related materials.

All-Electrochemical Nanofabrication of Stacked Ternary Metal Sulfide/Graphene Electrodes for High-Performance Alkaline Batteries.

Energy-storage materials can be assembled directly on the electrodes of a battery using electrochemical methods, this allowing sequential deposition, high structural control, and low cost. Here, a two-step approach combining electrophoretic deposition (EPD) and cathodic electrodeposition (CED) is demonstrated to fabricate multilayer hierarchical electrodes of reduced graphene oxide (rGO) and mixed transition metal sulfides (NiCoMnSx ). The process is performed directly on conductive electrodes applying a small electric bias to electro-deposit rGO and NiCoMnSx in alternated cycles, yielding an ideal porous network and a continuous path for transport of ions and electrons. A fully rechargeable alkaline battery (RAB) assembled with such electrodes gives maximum energy density of 97.2 Wh kg-1 and maximum power density of 3.1 kW kg-1 , calculated on the total mass of active materials, and outstanding cycling stability (retention 72% after 7000 charge/discharge cycles at 10 A g-1 ). When the total electrode mass of the cell is considered, the authors achieve an unprecedented gravimetric energy density of 68.5 Wh kg-1 , sevenfold higher than that of typical commercial supercapacitors, higher than that of Ni/Cd or lead-acid Batteries and similar to Ni-MH Batteries. The approach can be used to assemble multilayer composite structures on arbitrary electrode shapes.

Critical Role of Functional Groups Containing N, S, and O on Graphene Surface for Stable and Fast Charging Li-S Batteries.

Lithium-sulfur (Li-S) batteries are considered one of the most promising energy storage technologies, possibly replacing the state-of-the-art lithium-ion (Li-ion) batteries owing to their high energy density, low cost, and eco-compatibility. However, the migration of high-order lithium polysulfides (LiPs) to the lithium surface and the sluggish electrochemical kinetics pose challenges to their commercialization. The interactions between the cathode and LiPs can be enhanced by the doping of the carbon host with heteroatoms, however with relatively low doping content (<10%) in the bulk of the carbon, which can hardly interact with LiPs at the host surface. In this study, the grafting of versatile functional groups with designable properties (e.g., catalytic effects) directly on the surface of the carbon host is proposed to enhance interactions with LiPs. As model systems, benzene groups containing N/O and S/O atoms are vertically grafted and uniformly distributed on the surface of expanded reduced graphene oxide, fostering a stable interface between the cathode and LiPs. The combination of experiments and density functional theory calculations demonstrate improvements in chemical interactions between graphene and LiPs, with an enhancement in the electrochemical kinetics, power, and energy densities.

Selective deposition of metal oxide nanoflakes on graphene electrodes to obtain high-performance asymmetric micro-supercapacitors.

To meet the charging market demands of portable microelectronics, there has been a growing interest in high performance and low-cost microscale energy storage devices with excellent flexibility and cycling durability. Herein, interdigitated all-solid-state flexible asymmetric micro-supercapacitors (A-MSCs) were fabricated by a facile pulse current deposition (PCD) approach. Mesoporous Fe2O3 and MnO2 nanoflakes were functionally coated by electrodeposition on inkjet-printed graphene patterns as negative and positive electrodes, respectively. Our PCD approach shows significantly improved adhesion of nanostructured metal oxide with crack-free and homogeneous features, as compared with other reported electrodeposition approaches. The as-fabricated Fe2O3/MnO2 A-MSCs deliver a high volumetric capacitance of 110.6 F cm-3 at 5 µA cm-2 with a broad operation potential range of 1.6 V in neutral LiCl/PVA solid electrolyte. Furthermore, our A-MSC devices show a long cycle life with a high capacitance retention of 95.7% after 10 000 cycles at 100 µA cm-2. Considering its low cost and potential scalability to industrial levels, our PCD technique could be an efficient approach for the fabrication of high-performance MSC devices in the future.