Recent advances in MXene-based nanocomposites for supercapacitors.

MXene materials have become a competitive candidate for electrochemical energy storage due to their unique two-dimensional layered structure, high density, metal-like conductivity, fast ion intercalation, tunable surface terminal groups, and good mechanical flexibilities, showing unique application advantages in the field of supercapacitors. With widely research of MXene in energy storage applications, plenty of studies in synthesis strategies of MXene, including etching, intercalation and exfoliation processes, and its charge storage mechanism in supercapacitors have been conducted. However, the restacking of two-dimensional MXene nanosheets severely affects their electrochemical performance. To prevent the stacking of MXene, MXene-based nanocomposite electrode materials have been developed with remarkable electrochemical performance by incorporating conventional active capacitive materials, including metal oxides/sulfides and conductive polymers, with MXene. This review summarizes the etching strategies of MXenes and selection of intercalants, also discusses the charge storage mechanism of MXenes in aqueous and nonaqueous electrolytes. It mainly expounds the preparation strategies and applications of MXene-based nanocomposites in supercapacitors, including MXene/metal oxide, MXene/metal sulfide, MXene/conducting polymer, and MXene/carbon-based composites. Additionally, the advantages of combining MXene with other active materials in supercapacitor applications, which support its promising prospects, are discussed. Finally, the critical challenges faced by MXene-based nanocomposites in long-term research are mentioned.

Rapid Ion Transport Induced by the Enhanced Interaction in Composite Polymer Electrolyte for All-Solid-State Lithium-Metal Batteries.

High-quality solid electrolyte is the key to developing high-performance all-solid-state lithium-metal batteries (ASSLMBs). Herein, we report a thin composite polymer electrolyte (CPE) based on nanosized Li6.4La3Zr1.4Ta0.6O12 (N-LLZTO) and the PVDF-HFP matrix through a simple film-casting method. N-LLZTO induces partial dehydrofluorination of the poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrix that activates the coordination of Li+ with PVDF-HFP and LLZTO due to Lewis acid-base interactions, which facilitates dissociation of lithium salt to increase the Li+ carrier density. As a result, the as-fabricated composite polymer electrolyte with a 20 wt % N-LLZTO (CPE-20) membrane possesses high ionic conductivity (1.7 × 10-4 S cm-1), a high lithium-ion transference number (0.57), a wide electrochemical window (∼4.8 V), and good thermal stability. Moreover, the CPE-20 membrane displays excellent electrochemical stability to suppress the lithium dendrite and serves more than 2000 h. The solid-state Li|CPE-20|LiFePO4 pouch cells exhibit excellent cycling and rate performance, as well as high energy density. This study presents an effective strategy to design promising solid-state electrolyte for next-generation ASSLMBs.

Cationic intermediates assisted self-assembly two-dimensional Ti3C2Tx/rGO hybrid nanoflakes for advanced lithium-ion capacitors.

Two-dimensional (2D) material MXenes have been intensively concerned in energy-storage field due to these unique properties of metallic-like conductivity, good hydrophilicity and high volumetric capacity. However, the self-restocking of ultra-thin 2D materials seriously hinders these performances, which significantly inhibits the full exploitation of MXenes in the field of energy storage. To solve this issue, a strategy to prepare delaminated Ti3C2Tx (MXene) nanoflakes/reduced graphene oxide (rGO) composites is proposed using the electrostatic self-assembly between positively charged Ti3C2Tx with tetrabutylammonium ion (TBA+) modification and negatively charged graphene. The nanoflakes of Ti3C2Tx/rGO are well dispersed and arranged in a face-to-face structure to effectively alleviate the self-restacking and provide more electroactive sites for accessible of electrolyte ions. The prepared delaminated Ti3C2Tx/rGO anode shows a high reversible capacity up to 1394 mAh g-1 at a current density of 50 mA g-1. Moreover, a lithium-ion capacitor (LIC) was assembled with delaminated Ti3C2Tx/rGO anode and activated carbon (AC) cathode which can exhibit a specific capacity of 70.7 F g-1 at a current density of 0.1 A g-1 and deliver an ultrahigh energy density of 114 Wh kg-1 at a relatively high power density of 3125 W kg-1. These good electrochemical performances demonstrate the potential of delaminated Ti3C2Tx/rGO as an anode material for lithium-ion capacitors.

Scalable Production of Wearable Solid-State Li-Ion Capacitors from N-Doped Hierarchical Carbon.

Smart and wearable electronics have aroused substantial demand for flexible portable power sources, but it remains a large challenge to realize scalable production of wearable batteries/supercapacitors with high electrochemical performance and remarkable flexibility simultaneously. Here, a scalable approach is developed to prepare wearable solid-state lithium-ion capacitors (LICs) with superior performance enabled by synergetic engineering from materials to device architecture. Nitrogen-doped hierarchical carbon (HC) composed of 1D carbon nanofibers welded with 2D carbon nanosheets is synthesized via a unique self-propagating high-temperature synthesis (SHS) technique, which exhibits superior electrochemical performance. Subsequently, inspired by origami, here, wave-shaped LIC punch-cells based on the above materials are designed by employing a compatible and scalable post-imprint technology. Finite elemental analysis (FEA) confirms that the bending stress of the punch-cell can be offset effectively, benefiting from the wave architecture. The wearable solid-state LIC punch-cell exhibits large energy density, long cyclic stability, and superior flexibility. This study demonstrates great promise for scalable fabrication of wearable energy-storage systems.

High-performance solid-state Zn batteries based on a free-standing organic cathode and metal Zn anode with an ordered nano-architecture.

The increasing demand for large-scale manufacture of wearable electronics requires applicable energy storage devices with high-performance and safety. In this paper, we reported a solid-state Zn battery based on a free-standing organic cathode and metal Zn anode with an orderly aligned nano-architecture. The cathode is fabricated by depositing organic nanowire arrays on a carbon nanotube film via an in situ polymerization process, and the anode was prepared by electrodepositing Zn nanosheet arrays on carbon cloth. To avoid electrolyte leakage risks, a pseudo-solid-state PAAM-ZnSO4 gel electrolyte is employed, which is synthesized via a chemical cross-linking and film casting approach. The orderly aligned nanostructure of PANI nanowire arrays and zinc nanosheet arrays exhibits superior electrochemical performance, while the free-standing electrode configuration simplifies the battery fabrication process and offers excellent flexibility. The resulting solid-state Zn battery delivered a high capacity of 144 mA h g-1 at a current density of 0.2 A g-1, a 91.1% capacity retention after 150 cycles at a current density of 0.5 A g-1, and excellent flexibility under different bending states. This high-performance solid-state Zn battery provides a promising alternative energy storage device for next generation wearable electronics.

Rational design of nano-architecture composite hydrogel electrode towards high performance Zn-ion hybrid cell.

In this paper, we developed a novel Zn-ion hybrid cell based on a graphene-conducting polymer composite hydrogel (capacitor-type) cathode and a zinc metal (battery-type) anode. The pseudocapacitive-type cathode materials can effectively boost the capacity of Zn-ion hybrid cell compared to that of electrical double layer cathode materials. In particular, the composite hydrogel with rational designed three-dimensional (3D) nano-architecture combining 3D porous nanostructure with hydrogel, can significantly enlarge the active interfaces between the electrode and electrolyte. According to our experiments, the 3D graphene@PANI composite hydrogel electrode exhibits a large capacity of 154 mA h g-1, a superior rate capability and excellent capacity retention of 80.5% after 6000 charge-discharge cycles in a Zn-ion hybrid cell. The outstanding electrochemical properties demonstrate that the 3D nanostructure composite hydrogel materials can effectively promote the material utilization, transport of charges, and reduce the degradation of conducting polymers, leading to a highly efficient, fast and stable electrochemical process. Based on our results, Zn-ion hybrid cells based on a composite hydrogel electrode could be an extremely promising candidate for next generation electrochemical energy storage devices.

High-Performance Cable-Type Flexible Rechargeable Zn Battery Based on MnO2@CNT Fiber Microelectrode.

Nowadays, linear-shaped batteries have received increasing attentions because the unique one-dimensional architecture offers an omni-directional flexibility. We developed a cable-type flexible rechargeable Zn microbattery based on a microscale MnO2@carbon nanotube fiberlike composite cathode and Zn wire anode. The Zn-MnO2 cable microbattery exhibits a large specific capacity, good rate performance, and cyclic stability. The capacity of Zn-MnO2 cable batteries are 322 and 290 mAh/g based on MnO2 with aqueous and gel polymer electrolyte, corresponding to the specific energy of 437 and 360 Wh/kg, respectively. Besides, the Zn-MnO2 cable battery shows excellent flexibility, which can be folded into arbitrary shapes without sacrificing electrochemical performance. Furthermore, we studied electrochemical properties of Zn-MnO2 cable microbatteries with different Zn salt electrolytes, such as Zn salt with small anions (ZnSO4 or ZnCl2, etc.) and Zn salt with bulky anions (Zn(CF3SO3)2, etc.). With the merits of impressive electrochemical performance and flexibility, this first flexible rechargeable Zn-MnO2 cable-like battery presents a new approach to develop high-performance power sources for portable and wearable electronics.

Binder-free 2D titanium carbide (MXene)/carbon nanotube composites for high-performance lithium-ion capacitors.

Two-dimensional (2D) MXenes have a very good application prospect in the field of electrochemical energy storage due to their metallic conductivity, high volumetric capacity, mechanical and thermal stability. Herein, we report the preparation of titanium carbide (Ti3C2Tx)/carbon nanotube (CNT) flexible self-supporting composite films by vacuum filtration. The CNTs can effectively prevent Ti3C2Tx from stacking and improve the electrochemical performance. The as-fabricated Ti3C2Tx/CNT film shows a high reversible capacity of 489 mA h g-1 at a current density of 50 mA g-1 together with good cycling performance. The full-cell lithium-ion capacitor (LIC) is assembled using the Ti3C2Tx/CNT film as the anode and activated carbon as the cathode. The LIC exhibits a high energy density of 67 Wh kg-1 (based on the total weight of the anode and the cathode), and a good capacity retention of 81.3% after 5000 cycles. These results suggest that Ti3C2Tx-CNT films are promising as anode materials for lithium ion capacitors.

High Performance Lithium-Ion Hybrid Capacitors Employing Fe3O4-Graphene Composite Anode and Activated Carbon Cathode.

Lithium-ion capacitors (LICs) are considered as promising energy storage devices to realize excellent electrochemical performance, with high energy-power output. In this work, we employed a simple method to synthesize a composite electrode material consisting of Fe3O4 nanocrystallites mechanically anchored among the layers of three-dimensional arrays of graphene (Fe3O4-G), which exhibits several advantages compared with other traditional electrode materials, such as high Li storage capacity (820 mAh g-1 at 0.1 A g-1), high electrical conductivity, and improved electrochemical stability. Furthermore, on the basis of the appropriated charge balance between cathode and anode, we successfully fabricated Fe3O4-G//activated carbon (AC) soft-packaging LICs with a high energy density of 120.0 Wh kg-1, an outstanding power density of 45.4 kW kg-1 (achieved at 60.5 Wh kg-1), and an excellent capacity retention of up to 94.1% after 1000 cycles and 81.4% after 10 000 cycles. The energy density of the Fe3O4-G//AC hybrid device is comparable with Ni-metal hydride batteries, and its capacitive power capability and cycle life is on par with supercapacitors (SCs). Therefore, this lithium-ion hybrid capacitor is expected to bridge the gap between Li-ion battery and SCs and gain bright prospects in next-generation energy storage fields.

Scalable Self-Propagating High-Temperature Synthesis of Graphene for Supercapacitors with Superior Power Density and Cyclic Stability.

An ultrafast self-propagating high-temperature synthesis technique offers scalable routes for the fabrication of mesoporous graphene directly from CO2 . Due to the excellent electrical conductivity and high ion-accessible surface area, supercapacitor electrodes based on the obtained graphene exhibit superior energy and power performance. The capacitance retention is higher than 90% after one million charge/discharge cycles.

Chemically Crosslinked Hydrogel Film Leads to Integrated Flexible Supercapacitors with Superior Performance.

A high-strength poly(vinyl alcohol) chemical hydrogel (PCH) film is prepared by coupling covalent crosslinking with a film-casting process. Conducting polyaniline (PANI) is then embedded in the PCH film by in situ growth to form a composite film with a PANI-hydrogel-PANI configuration, which leads to a new conceptual flexible supercapacitor with all-in-one configuration that exhibits superior electrochemical performance and mechanical flexibility.

Ethylene Glycol Intercalated Cobalt/Nickel Layered Double Hydroxide Nanosheet Assemblies with Ultrahigh Specific Capacitance: Structural Design and Green Synthesis for Advanced Electrochemical Storage.

Because of the rapid depletion of fossil fuels and severe environmental pollution, more advanced energy-storage systems need to possess dramatically improved performance and be produced on a large scale with high efficiency while maintaining low-enough costs to ensure the higher and wider requirements. A facile, energy-saving process was successfully adopted for the synthesis of ethylene glycol intercalated cobalt/nickel layered double hydroxide (EG-Co/Ni LDH) nanosheet assembly variants with higher interlayer distance and tunable transitional-metal composition. At an optimized starting Co/Ni ratio of 1, the nanosheet assemblies display a three-dimensional, spongelike network, affording a high specific surface area with advantageous mesopore structure in 2-5 nm containing large numbers of about 1.2 nm micropores for promoting electrochemical reaction. An unprecedented electrochemical performance was achieved, with a specific capacitance of 4160 F g(-1) at a discharge current density of 1 A g(-1) and of 1313 F g(-1) even at 50 A g(-1), as well as excellent cycling ability. The design and optimization of EG-Co/Ni LDH nanosheets in compositions, structures, and performances, in conjunction with the easy and relatively "green" synthetic process, will play a pivotal role in meeting the needs of large-scale manufacture and widespread application for advanced electrochemical storage.

Shape-controlled synthesis of nanocarbons through direct conversion of carbon dioxide.

Morphology control of carbon-based nanomaterials (nanocarbons) is critical to practical applications because their physical and chemical properties are highly shape-dependent. The discovery of novel shaped nanocarbons stimulates new development in carbon science and technology. Based on direct reaction of CO2 with Mg metal, we achieved controlled synthesis of several different types of nanocarbons including mesoporous graphene, carbon nanotubes, and hollow carbon nanoboxes. The last one, to our knowledge, has not been previously reported to this date. The method described here allows effective control of the shape and dimensions of nanocarbons through manipulation of reaction temperature. The formation mechanism of nanocarbons is proposed. As a proof of concept, the synthesized nanocarbons are used for electrodes in symmetrical supercapacitors, which exhibit high capacitance and good cycling stability. The reported protocols are instructive to production of nanocarbons with controlled shape and dimensions which are much desirable for many practical applications.

Large-scale production of nanographene sheets with a controlled mesoporous architecture as high-performance electrochemical electrode materials.

Graphene is considered as a rising-star material because of its unique properties and it is a promising material for applications in many fields. In recent years, experiments on graphene fabricated by using versatile methods have shed light on the crucial problem of aggregation and restacking, which is induced by strong π-π stacking and van der Waals forces, but preparation methods for real-world applications are still a great challenge. Here we report a facile, rapid, and environmentally friendly process, the burn-quench method, that allows large-scale and controlled synthesis of ordered mesoporous nanographene with 1-5 layers, which has a high surface area and electric conductivity. Electrodes composed of nanographene with a mesoporous architecture used both in electrochemical capacitors and lithium-ion batteries have a high specific capacitance, rate capability, energy density, and cyclic stability. Our results represent an important step toward large-scale graphene synthesis based on this new burn-quench method for applications in high-performance electrochemical energy storage devices.

One-step electrophoretic deposition of reduced graphene oxide and Ni(OH)2 composite films for controlled syntheses supercapacitor electrodes.

A facile, rapid, scalable, and environmentally friendly electrophoretic deposition (EPD) approach has been developed for the fabrication of reduced graphene oxide (RGO) and Ni(OH)(2) syntheses based on EPD of graphene oxide (GO) and Ni(NO(3))(2) colloidal suspension. Nickel ion decoration made GO positively charged and further made cathodic EPD feasible. Direct assembly by one-step EPD facilitated transformation from GO to RGO and resulted in multilayer or flower-like RGO/Ni(OH)(2) hybrid films on different substrates. X-ray diffraction analysis suggested that the crystal structures of Ni(OH)(2) depended on the colloidal suspension and the substrate. Further transmission electron microscopy characterization indicated that Ni(OH)(2) nanoclusters composed of 5-10 nm nanoparticles in grain size were homogeneously dispersed and anchored on the RGO. The resulting 100% binder-free RGO/Ni(OH)(2) electrodes exhibited excellent pseudocapacitive behavior with high specific capacitance of 1404 F g(-1) at 2 A g(-1), high rate capability, and good electrochemical cyclic stability. These results paved the way for EPD to produce RGO-based nanocomposite films for high-performance energy storage devices.

The synthesis and photoluminescence properties of selenium-treated porous silicon nanowire arrays.

Here we prepared vertical and single crystalline porous silicon nanowire (SiNW) arrays using the silver-assisted electroless etching method. The selenization was carried out by annealing the samples in vacuum with selenium atmosphere. The selenization treatment at 700 °C is useful for investigating the photoluminescence (PL) properties of porous SiNWs, with an enhancement of 30 times observed. The observed PL peaks blue-shift to 650 nm and the decomposition of the spectrum reveals that three PL bands with different origins are obtained. It is proved that selenization treatment could remove the Si-H bonds on the surface and form Si-Se bonds, which could increase the absorbance of the SiNWs and also enhance the stability of the PL intensity. These Se-treated porous SiNWs may be useful as nanoscale optoelectronic devices.

Synthesis and Photoluminescence Properties of Porous Silicon Nanowire Arrays.

Herein, we prepare vertical and single crystalline porous silicon nanowires (SiNWs) via a two-step metal-assisted electroless etching method. The porosity of the nanowires is restricted by etchant concentration, etching time and doping lever of the silicon wafer. The diffusion of silver ions could lead to the nucleation of silver nanoparticles on the nanowires and open new etching ways. Like porous silicon (PS), these porous nanowires also show excellent photoluminescence (PL) properties. The PL intensity increases with porosity, with an enhancement of about 100 times observed in our condition experiments. A "red-shift" of the PL peak is also found. Further studies prove that the PL spectrum should be decomposed into two elementary PL bands. The peak at 850 nm is the emission of the localized excitation in the nanoporous structure, while the 750-nm peak should be attributed to the surface-oxidized nanostructure. It could be confirmed from the Fourier transform infrared spectroscopy analyses. These porous SiNW arrays may be useful as the nanoscale optoelectronic devices.

[The dose-effect relationship of water fluoride levels and renal damage in children].

OBJECTIVE: To explore the dose-effect relationship of water fluoride levels and renal damage in children and observe the difference of renal function between high-loaded fluoride people and dental fluorosis people in the same water fluoride level region. METHODS: 210 children were divided into seven groups in term of drinking water fluoride levels and whether they suffered from dental fluorosis. Fluoride concentrations in urine and serum and activities of urine NAG and gamma-GT were determined. RESULTS: The urine and serum fluoride of high-loaded fluoride people and dental fluorosis people increased compared with control, moreover fluoride contents in urine and serum increased gradually with the increase of fluoride level in drinking water. Urine NAG and gamma-GT activities significantly increased in dental fluorosis people from area of 2.58 mg/L fluoride in drinking water and in those two groups from area of 4.51 mg/L fluoride in drinking water. Moreover, there existed an obvious dose-effect relationship between the drinking water fluoride concentration and NAG and gamma-GT activity. CONCLUSION: Over 2.0 mg/L fluoride in drinking water can cause renal damage in children, and the damage degree increases with the drinking water fluoride content. Renal damage degree is not related to whether the children suffered from dental fluorosis and mainly due to water fluoride concentration.