Shuanghao Zheng

Stacked-Layer Heterostructure Films of 2D Thiophene Nanosheets and Graphene for High-Rate All-Solid-State Pseudocapacitors with Enhanced Volumetric Capacitance

Stacked-layer heterostructure films of 2D thiophene nanosheets and electrochemically exfoliated graphene are constructed for ultrahigh-rate all-solid-state flexible pseudocapacitors and micro-supercapacitors with superior volumetric capacitance due to the synergetic effect of the ultrathin pseudocapacitive thiophene nanosheets and the capacitive electrochemically exfoliated graphene.

Ti3C2 MXene-Derived Sodium/Potassium Titanate Nanoribbons for High-Performance Sodium/Potassium Ion Batteries with Enhanced Capacities

Sodium and potassium ion batteries hold promise for next-generation energy storage systems due to their rich abundance and low cost, but are facing great challenges in optimum electrode materials for actual applications. Here, ultrathin nanoribbons of sodium titanate (M-NTO, NaTi1.5O8.3) and potassium titanate (M-KTO, K2Ti4O9) were successfully synthesized by a simultaneous oxidation and alkalization process of Ti3C2 MXene. Benefiting from the suitable interlayer spacing (0.90 nm for M-NTO, 0.93 nm for M-KTO), ultrathin thickness (<11 nm), narrow widths of nanoribbons (<60 nm), and open macroporous structures for enhanced ion insertion/extraction kinetics, the resulting M-NTO exhibited a large reversible capacity of 191 mAh g-1 at 200 mA g-1 for sodium storage, higher than those of pristine Ti3C2 (178 mAh g-1) and commercial TiC derivatives (86 mAh g-1). Notably, M-KTO displayed a superior reversible capacity of 151 mAh g-1 at 50 mA g-1 and 88 mAh g-1 at a high rate of 300 mA g-1 and long-term stable cyclability over 900 times, which outperforms other Ti-based layered materials reported to date. Moreover, this strategy is facile and highly flexible and can be extended for preparing a large number of MXene-derived materials, from the 60+ group of MAX phases, for various applications such as supercapacitors, batteries, and electrocatalysts.

Bottom-Up Fabrication of Sulfur-Doped Graphene Films Derived from Sulfur-Annulated Nanographene for Ultrahigh Volumetric Capacitance Micro-Supercapacitors

Heteroatom doping of nanocarbon films can efficiently boost the pseudocapacitance of micro-supercapacitors (MSCs); however, wafer-scale fabrication of sulfur-doped graphene films with a tailored thickness and homogeneous doping for MSCs remains a great challenge. Here we demonstrate the bottom-up fabrication of continuous, uniform, and ultrathin sulfur-doped graphene (SG) films, derived from the peripherical trisulfur-annulated hexa-peri-hexabenzocoronene (SHBC), for ultrahigh-rate MSCs (SG-MSCs) with landmark volumetric capacitance. The SG film was prepared by thermal annealing of the spray-coated SHBC-based film, with assistance of a thin Au protecting layer, at 800 °C for 30 min. SHBC with 12 phenylthio groups decorated at the periphery is critical as a precursor for the formation of the continuous and ultrathin SG film, with a uniform thickness of ∼10.0 nm. Notably, the as-produced all-solid-state planar SG-MSCs exhibited a highly stable pseudocapacitive behavior with a volumetric capacitance of ∼582 F cm-3 at 10 mV s-1, excellent rate capability with a remarkable capacitance of 8.1 F cm-3 even at an ultrahigh rate of 2000 V s-1, ultrafast frequency response with a short time constant of 0.26 ms, and ultrahigh power density of ∼1191 W cm-3. It is noteworthy that these values obtained are among the best values for carbon-based MSCs reported to date.

One-Step Device Fabrication of Phosphorene and Graphene Interdigital Micro-Supercapacitors with High Energy Density

Rational engineering and simplified fabrication of high-energy micro-supercapacitors (MSCs) using graphene and other 2D nanosheets are of great value for flexible and integrated electronics. Here we develop one-step mask-assisted simplified fabrication of high-energy MSCs (PG-MSCs) based on the interdigital hybrid electrode (PG) patterns of stacking high-quality phosphorene nanosheets and electrochemically exfoliated graphene in ionic liquid electrolyte. The hybrid PG films with interdigital patterns were directly manufactured by layer-by-layer deposition of phosphorene and graphene nanosheets with the assistance of a customized interdigital mask, and directly transferred onto a flexible substrate. The resultant patterned PG films present outstanding uniformity, flexibility, conductivity (319 S cm-1), and structural integration, which can directly serve as binder- and additive-free flexible electrodes for MSCs. Remarkably, PG-MSCs deliver remarkable energy density of 11.6 mWh cm-3, outperforming most nanocarbon-based MSCs. Moreover, our PG-MSCs show outstanding flexibility and stable performance with slight capacitance fluctuation even under highly folded states. In addition, our simplified mask-assisted strategy for PG-MSCs is highly flexible for simplified production of parallelly and serially interconnected modular power sources, without need of conventional metal-based interconnects and contacts, for designable integrated circuits with high output current and voltage.

Scalable Fabrication of Photochemically Reduced Graphene-Based Monolithic Micro-Supercapacitors with Superior Energy and Power Densities

Micro-supercapacitors (MSCs) hold great promise as highly competitive miniaturized power sources satisfying the increased demand of smart integrated electronics. However, single-step scalable fabrication of MSCs with both high energy and power densities is still challenging. Here we demonstrate the scalable fabrication of graphene-based monolithic MSCs with diverse planar geometries and capable of superior integration by photochemical reduction of graphene oxide/TiO2 nanoparticle hybrid films. The resulting MSCs exhibit high volumetric capacitance of 233.0 F cm-3, exceptional flexibility, and remarkable capacity of modular serial and parallel integration in aqueous gel electrolyte. Furthermore, by precisely engineering the interface of electrode with electrolyte, these monolithic MSCs can operate well in a hydrophobic electrolyte of ionic liquid (3.0 V) at a high scan rate of 200 V s-1, two orders of magnitude higher than those of conventional supercapacitors. More notably, the MSCs show landmark volumetric power density of 312 W cm-3 and energy density of 7.7 mWh cm-3, both of which are among the highest values attained for carbon-based MSCs. Therefore, such monolithic MSC devices based on photochemically reduced, compact graphene films possess enormous potential for numerous miniaturized, flexible electronic applications.

High Packing Density Unidirectional Arrays of Vertically Aligned Graphene with Enhanced Areal Capacitance for High-Power Micro-Supercapacitors

Interfacial integration of a shape-engineered electrode with a strongly bonded current collector is the key for minimizing both ionic and electronic resistance and then developing high-power supercapacitors. Herein, we demonstrated the construction of high-power micro-supercapacitors (VG-MSCs) based on high-density unidirectional arrays of vertically aligned graphene (VG) nanosheets, derived from a thermally decomposed SiC substrate. The as-grown VG arrays showed a standing basal plane orientation grown on a (0001̅) SiC substrate, tailored thickness (3.5-28 μm), high-density structurally ordering alignment of graphene consisting of 1-5 layers, vertically oriented edges, open intersheet channels, high electrical conductivity (192 S cm-1), and strong bonding of the VG edges to the SiC substrate. As a result, the demonstrated VG-MSCs displayed a high areal capacitance of ∼7.3 mF cm-2 and a fast frequency response with a short time constant of 9 ms. Furthermore, VG-MSCs in both an aqueous polymer gel electrolyte and nonaqueous ionic liquid of 1-ethyl-3-methylimidazolium tetrafluoroborate operated well at high scan rates of up to 200 V s-1. More importantly, VG-MSCs offered a high power density of ∼15 W cm-3 in gel electrolyte and ∼61 W cm-3 in ionic liquid. Therefore, this strategy of producing high-density unidirectional VG nanosheets directly bonded on a SiC current collector demonstrated the feasibility of manufacturing high-power compact supercapacitors.

Graphene-Based Linear Tandem Micro-Supercapacitors with Metal-Free Current Collectors and High-Voltage Output

Printable supercapacitors are regarded as a promising class of microscale power source, but are facing challenges derived from conventional sandwich-like geometry. Herein, the printable fabrication of new-type planar graphene-based linear tandem micro-supercapacitors (LTMSs) on diverse substrates with symmetric and asymmetric configuration, high-voltage output, tailored capacitance, and outstanding flexibility is demonstrated. The resulting graphene-based LTMSs consisting of 10 micro-supercapacitors (MSs) present efficient high-voltage output of 8.0 V, suggestive of superior uniformity of the entire integrated device. Meanwhile, LTMSs possess remarkable flexibility without obvious capacitance degradation under different bending states. Moreover, areal capacitance of LTMSs can be sufficiently modulated by incorporating polyaniline-based pseudocapacitive nanosheets into graphene electrodes, showing enhanced capacitance of 7.6 mF cm-2 . To further improve the voltage output and energy density, asymmetric LTMSs are fabricated through controlled printing of linear-patterned graphene as negative electrodes and MnO2 nanosheets as positive electrodes. Notably, the asymmetric LTMSs from three serially connected MSs are easily extended to 5.4 V, triple voltage output of the single cell (1.8 V), suggestive of the versatile applicability of this technique. Therefore, this work offers numerous opportunities of graphene and analogous nanosheets for one-step scalable fabrication of flexible tandem energy storage devices integrating with printed electronics on same substrate.

All-MXene-Based Integrated Electrode Constructed by Ti3C2 Nanoribbon Framework Host and Nanosheet Interlayer for High-Energy-Density Li–S Batteries

High-energy-density lithium-sulfur (Li-S) batteries hold promise for next-generation portable electronic devices, but are facing great challenges in rational construction of high-performance flexible electrodes and innovative cell configurations for actual applications. Here we demonstrated an all-MXene-based flexible and integrated sulfur cathode, enabled by three-dimensional alkalized Ti3C2 MXene nanoribbon (a-Ti3C2 MNR) frameworks as a S/polysulfides host (a-Ti3C2-S) and two-dimensional delaminated Ti3C2 MXene (d-Ti3C2) nanosheets as interlayer on a polypropylene (PP) separator, for high-energy and long-cycle Li-S batteries. Notably, an a-Ti3C2 MNR framework with open interconnected macropores and an exposed surface area guarantees high S loading and fast ionic diffusion for prompt lithiation/delithiation kinetics, and the 2D d-Ti3C2 MXene interlayer remarkably prevents the shuttle effect of lithium polysulfides via both chemical absorption and physical blocking. As a result, the integrated a-Ti3C2-S/d-Ti3C2/PP electrode was directly used for Li-S batteries, without the requirement of a metal current collector, and exhibited a high reversible capacity of 1062 mAh g-1 at 0.2 C and enhanced capacity of 632 mAh g-1 after 50 cycles at 0.5 C, outperforming the a-Ti3C2-S/PP electrode (547 mAh g-1) and conventional a-Ti3C2-S on an Al current collector (a-Ti3C2-S/Al) (597 mAh g-1). Furthermore, the all-MXene-based integrated cathode displayed outstanding rate capacity of 288 mAh g-1 at 10 C and long-life cyclability. Therefore, this proposed strategy of constructing an all-MXene-based cathode can be readily extended to assemble a large number of MXene-derived materials, from a group of 60+ MAX phases, for applications such as various batteries and supercapacitors.

2D transition metal carbide MXene as a robust biosensing platform for enzyme immobilization and ultrasensitive detection of phenol

MXene-Ti3C2, as a new class of two-dimensional (2D) transition metal carbides (or nitrides), has been synthesized by exfoliating pristine Ti3AlC2 phases with hydrofluoric acid. The SEM and XRD images show that the resultant MXene possesses a graphene-like 2D nanostructure. and the surface of MXene has been partially terminated with -OH, thus providing a favorable microenvironment for enzyme immobilization and retaining their bioactivity and stability. Considering the unique metallic conductivity, biocompatibility and good dispersion in aqueous phase, the as-prepared MXene was explored as a new matrix to immobilize tyrosinase (a model enzyme) for fabricating a mediator-free biosensor for ultrasensitive and rapid detection of phenol. The varying electrochemical measurements were used to investigate the electrochemical performance of MXene-based tyrosinase biosensors. The results revealed that the direct electron transfer between tyrosinase and electrode could be easily achieved via a surface-controlled electrochemical process. The fabricated MXene-based tyrosinase biosensors exhibited good analytical performance over a wide linear range from 0.05 to 15.5 μmol L-1, with a low detection limit of 12 nmol L-1 and a sensitivity of 414.4 mA M-1. The proposed biosensing approach also demonstrated good repeatability, reproducibility, long-term stability and high recovery for phenol detection in real water samples. With those excellent performances, MXene with graphene-like structure is proved to be a robust and versatile electrochemical biosensing platform for enzyme-based biosensors and biocatalysis, and has wide potential applications in biomedical detection and environmental analysis.

All-solid-state flexible planar lithium ion micro-capacitors

The ever-increasing boom in smart, miniaturized electronics has led to an urgent need for on-chip energy storage systems that exhibit high performance, safety, flexibility and robust integration. However, tremendous challenges exist. Here, we demonstrate the first prototype of all-solid-state planar lithium ion micro-capacitors (LIMCs) based on interdigital patterns of lithium titanate nanospheres as the anode and activated graphene as the cathode. The interdigital LIMCs were fabricated via layer-by-layer mask-assisted deposition of graphene and electrode materials, without the need for metal current collectors, additives or polymer binders. The as-assembled LIMCs delivered a record volumetric energy density of 53.5 mW h cm−3. Furthermore, they exhibited outstanding mechanical flexibility without performance degradation under repeated bending, superior electrochemical metrics and safety at a high temperature of 80 °C due to the highly stable ionogel electrolyte and the absence of a separator. Additionally, our microdevices presented remarkable modular integration of the constructed bipolar cells for boosting high voltage and capacitance. Therefore, these LIMCs hold great potential for application in future flexible and wearable electronics.