Molecular Tailoring of an n/p-type Phenothiazine Organic Scaffold for Zinc Batteries.

The p-type or n-type redox reactions of organics are being used as the reversible electrodes to build the next-generation rechargeable batteries with sustainable and tunable characteristics. However, the n-type organics that store cations generally exhibit low potential (<0.8 V vs. Zn/Zn2+ ), while the p-type organics that store anions suffer from limited capacity (<100 mAh g-1 ). Herein, we demonstrate that bis(phenylamino)phenothiazin-5-ium iodide (PTD-1) containing both n-type and p-type redox moieties exhibits a hybrid charge storage mechanism (n/p-type at low potential, p-type at high potential). Such a hybrid mechanism combines the advantages of n- and p-type reactions and compensates for the associated drawbacks of each. Accordingly, the aqueous Zn//PTD-1 full cell shows a high voltage (1.8 Vmaximum or 1.1 Vaverage ), a high capacity 188.24 mAh gPTD-1 -1 (achieved at 40 mA g-1 ), a long-life and a supercapacitor-like high power. These results shed new light on the design of advanced organic electrodes.

Progress of Organic Electrodes in Aqueous Electrolyte for Energy Storage and Conversion.

Aqueous batteries using inorganic compounds as electrode materials are considered a promising solution for grid-scale energy storage, while wide application is limited by the short life and/or high cost of electrodes. Organics with carbonyl groups are being investigated as the alternative to inorganic electrode materials because they offer the advantages of tunable structures, renewability, and they are environmentally benign. Furthermore, the wide internal space of such organic materials enables flexible storage of various charged ions (for example, H+ , Li+ , Na+ , K+ , Zn2+ , Mg2+ , and Ca2+ , and so on). We offer a comprehensive overview of the progress of organics containing carbonyls for energy storage and conversion in aqueous electrolytes, including applications in aqueous batteries as solid-state electrodes, in flow batteries as soluble redox species, and in water electrolysis as redox buffer electrodes. The advantages of organic electrodes are summarized, with a discussion of the challenges remaining for their practical application.

Zinc-Organic Battery with a Wide Operation-Temperature Window from -70 to 150 °C.

Aqueous zinc (Zn) batteries have been considered as promising candidates for grid-scale energy storage. However, their cycle stability is generally limited by the structure collapse of cathode materials and dendrite formation coupled with undesired hydrogen evolution on the Zn anode. Herein we propose a zinc-organic battery with a phenanthrenequinone macrocyclic trimer (PQ-MCT) cathode, a zinc-foil anode, and a non-aqueous electrolyte of a N,N-dimethylformamide (DMF) solution containing Zn2+ . The non-aqueous nature of the system and the formation of a Zn2+ -DMF complex can efficiently eliminate undesired hydrogen evolution and dendrite growth on the Zn anode, respectively. Furthermore, the organic cathode can store Zn2+ ions through a reversible coordination reaction with fast kinetics. Therefore, this battery can be cycled 20 000 times with negligible capacity fading. Surprisingly, this battery can even be operated in a wide temperature range from -70 to 150 °C.

Organic Proton-Buffer Electrode to Separate Hydrogen and Oxygen Evolution in Acid Water Electrolysis.

Hydrogen production from water via electrolysis in acid is attracting extensive attention as an attractive alternative approach to replacing fossil fuels. However, the simultaneous evolution of H2 and O2 requires a fluorine-containing proton exchange membrane to prevent the gases from mixing while using the same space to concentrate the gases, which significantly increases the cost and reduces the flexibility of this approach. Here, a battery electrode based on the highly reversible enolization reaction of pyrene-4,5,9,10-tetraone is first introduced as a solid-state proton buffer to separate the O2 and H2 evolution of acidic water electrolysis in space and time, through which the gas mixing issue can be avoided without using any membrane. This process allows us to separately consider H2 and O2 production according to the variation in input power (e.g., the renewable energy) and/or the location for H2 concentration, thus showing high flexibility for H2 production.

An Environmentally Friendly and Flexible Aqueous Zinc Battery Using an Organic Cathode.

Rechargeable batteries have been used to power various electric devices and store energy from renewables, but their toxic components (namely, electrode materials, electrolyte, and separator) generally cause serious environment issues when disused. Such toxicity characteristic makes them difficult to power future wearable electronic devices. Now an environmentally friendly and highly safe rechargeable battery, based on a pyrene-4,5,9,10-tetraone (PTO) cathode and zinc anode in mild aqueous electrolyte is presented. The PTO-cathode shows a high specific capacity (336 mAh g-1 ) for Zn2+ storage with fast kinetics and high reversibility. Thus, the PTO//Zn full cell exhibits a high energy density (186.7 Wh kg-1 ), supercapacitor-like power behavior and long-term lifespan (over 1000 cycles). Moreover, a belt-shaped PTO//Zn battery with robust mechanical durability and remarkable flexibility is first fabricated to clarify its potential application in wearable electronic devices.

A 1T'-MoTe2/GaN van der Waals Schottky junction for self-powered UV imaging and optical communication.

Schottky-type self-powered UV photodetectors are promising for next-generation imaging systems. Nevertheless, conventional device fabrication using high-energy metal deposition brings unintentional interface defects, leading to deteriorated device performance and inhomogeneities. Emerging two-dimensional (2D) metallic materials offer an alternative pathway to overcoming such limitations because of their naturally passivated surfaces and the ease of combining with mature bulk semiconductors via van der Waals (vdW) integration. Here, we report the controllable preparation of MoTe2 in the pure 1T' phase and the fabrication of a high-performance 1T'-MoTe2/GaN vdW Schottky photodiode. With the reduced interface states and suppressed dark current as low as 20 pA at zero bias, the photodiode exhibits a remarkable UV-to-visible (R350/R400) rejection ratio of 1.6 × 104, a stable photoresponsivity of ∼50 mA W-1 and a detectivity of 3.5 × 1012 Jones under 360 nm illumination. The photocurrent ON/OFF ratio reaches ∼4.9 × 106 under 10.5 mW irradiation (360 nm). In particular, the 1T'-MoTe2/GaN Schottky diode shows excellent weak-light detection capability, which could detect a 3 nW 360 nm laser and the light emission from a lighter with a pronounced Ilight/Idark ratio of ∼2. Finally, the applications of the device in self-powered UV imaging and optical communication are demonstrated. These results reveal the great prospects of 2D/3D integration in multifunctional optoelectronics, which may inspire novel 2D-related devices and expand their applications in widespread fields.

Solution-processed thickness engineering of tellurene for field-effect transistors and polarized infrared photodetectors.

Research on elemental 2D materials has been experiencing a renaissance in the past few years. Of particular interest is tellurium (Te), which possesses many exceptional properties for nanoelectronics, photonics, and beyond. Nevertheless, the lack of a scalable approach for the thickness engineering and the local properties modulation remains a major obstacle to unleashing its full device potential. Herein, a solution-processed oxidative etching strategy for post-growth thickness engineering is proposed by leveraging the moderate chemical reactivity of Te. Large-area ultrathin nanosheets with well-preserved morphologies could be readily obtained with appropriate oxidizing agents, such as HNO2, H2O2, and KMnO4. Compared with the conventional physical thinning approaches, this method exhibits critical merits of high efficiency, easy scalability, and the capability of site-specific thickness patterning. The thickness reduction leads to substantially improved gate tunability of field-effect transistors with an enhanced current switching ratio of ∼103, promoting the applications of Te in future logic electronics. The response spectrum of Te phototransistors covers the full range of short-wave infrared wavelength (1-3 µm), and the room-temperature responsivity and detectivity reach 0.96 AW-1 and 2.2 × 109 Jones at the telecom wavelength of 1.55 µm, together with a favorable photocurrent anisotropic ratio of ∼2.9. Our study offers a new approach to tackling the thickness engineering issue for solution-grown Te, which could help realize the full device potential of this emerging p-type 2D material.

An organic/inorganic electrode-based hydronium-ion battery.

Hydronium-ion batteries are regarded as one of the most promising energy technologies as next-generation power sources, benefiting from their cost effectivity and sustainability merits. Herein, we propose a hydronium-ion battery which is based on an organic pyrene-4,5,9,10-tetraone anode and an inorganic MnO2@graphite felt cathode in an acid electrolyte. Its operation involves a quinone/hydroquinone redox reaction on anode and a MnO2/Mn2+ conversion reaction on cathode, in parallel with the transfer of H3O+ between two electrodes. The distinct operation mechanism affords this hydronium-ion battery an energy density up to 132.6 Wh kg-1 and a supercapacitor-comparable power density of 30.8 kW kg-1, along with a long-term cycling life over 5000 cycles. Furthermore, surprisingly, this hydronium-ion battery works well even with a frozen electrolyte under -40 °C, and superior rate performance and cycle stability remain at -70 °C.

Binding Zinc Ions by Carboxyl Groups from Adjacent Molecules toward Long-Life Aqueous Zinc-Organic Batteries.

The newly emerged aqueous Zn-organic batteries are attracting extensive attention as a promising candidate for energy storage. However, most of them suffer from the unstable and/or soluble nature of organic molecules, showing limited cycle life (≤3000 cycles) that is far away from the requirement (10 000 cycles) for grid-scale energy storage. Here, a new aqueous zinc battery is proposed by using sulfur heterocyclic quinone dibenzo[b,i]thianthrene-5,7,12,14-tetraone (DTT) as the cathode. The cell shows a high reversible capacity of 210.9 mAh gDTT -1 at 50 mA gDTT -1 with a high mass loading of 5 mgDTT cm-2 , along with a fast kinetics for charge storage. Electrochemical measurements, ex situ analyses, and density functional theory calculation successfully demonstrate that the DTT electrode can simultaneously store both protons (H+ ) and Zn2+ to form DTT2 (H+ )4 (Zn2+ ), where Zn2+ is bound to the carboxyl groups from the adjacent DTT molecules with improved stability. Benefitting from the improved molecular stability and the inherent low solubility of DTT and related discharge products, the DTT//Zn full cell exhibits a superlong life of 23 000 cycles with a capacity retention of 83.8%, which is much superior to previous reports.

Organic Cathode Materials for Rechargeable Zinc Batteries: Mechanisms, Challenges, and Perspectives.

Energy and environmental issues have given rise to the development of advanced energy-storage devices worldwide. Electrochemical energy technologies, such as rechargeable batteries, are considered to be the most reliable and efficient candidates. Compared with other batteries, zinc-based batteries seem promising due to their advantages, including inherent safety, cost-effectiveness, and environmentally friendliness. As potential alternatives to conventional inorganic cathodes, organic cathodes for Zn-organic batteries have become a hot topic for research, owing to their favorable characteristics, such as easy structure design, controllable synthesis, and environmental benignancy. Herein, a systematic overview on the fundamentals of organic cathode materials for zinc batteries, including material design, electrochemical mechanisms, technical advances, and challenging analysis, is provided. Furthermore, perspectives and corresponding research directions are offered to facilitate the future development of organic cathode materials for zinc batteries toward practical applications.

Low-cost and high safe manganese-based aqueous battery for grid energy storage and conversion.

As an effective energy storage technology, rechargeable batteries have long been considered as a promising solution for grid integration of intermittent renewables (such as solar and wind energy). However, their wide application is still limited by safety issue and high cost. Herein, a new battery chemistry is proposed to satisfy the requirements of grid energy storage. We report a simple Cu-Mn battery, which is composed of two separated current collectors in an H2SO4-CuSO4-MnSO4 electrolyte without using any membrane. The Cu-Mn battery shows an energy density of 40.8 Wh L-1, a super-long life of 10,000 cycles (without obvious capacity decay) and negligible self-discharge. And the capital cost of US$ 11.9 kWh-1 based on electrolyte is lower than any previous batteries. More importantly, the battery can still work smoothly during thermal abuse test and drill-through test, showing high safe nature. Furthermore, a combination system integrating the Cu-Mn battery and hydrogen evolution is also proposed, which is able to avoid the generation of explosive H2/O2 mixture, and presents an efficient approach for grid energy storage and conversion.

Integrating Desalination and Energy Storage using a Saltwater-based Hybrid Sodium-ion Supercapacitor.

Ever-increasing freshwater scarcity and energy crisis problems require efficient seawater desalination and energy storage technologies; however, each target is generally considered separately. Herein, a hybrid sodium-ion supercapacitor, involving a carbon-coated nano-NaTi2 (PO4 )3 -based battery anode and an activated-carbon-based capacitive cathode, is developed to combine desalination and energy storage in one device. On charge, the supercapacitor removes salt in a flowing saltwater electrolyte through Cl- electrochemical adsorption at the cathode and Na+ intercalation at the anode. Discharge delivers useful electric energy and regenerates the electrodes. This supercapacitor can be used not only for energy storage with promising electrochemical performance (i.e., high power, high efficiency, and long cycle life), but also as a desalination device with desalination capacity of 146.8 mg g-1 , much higher than most reported capacitive and battery desalination devices. Finally, we demonstrate renewables to usable electric energy and desalted water through combining commercial photovoltaics and this hybrid supercapacitor.

A clean and membrane-free chlor-alkali process with decoupled Cl2 and H2/NaOH production.

Existing chlor-alkali processes generally use asbestos, mercury or fluorine-containing ion-exchange membranes to separate the simultaneous chlorine production on the anode and hydrogen production on the cathode, and form sodium hydroxide in the electrolyte. Here, using the Na+ de-intercalation/intercalation of a Na0.44MnO2 electrode as a redox mediator, we decouple the chlor-alkali process into two independent steps: a H2 production step with the NaOH formation in the electrolyte and a Cl2 production step. The first step involves a cathodic H2 evolution reaction (H2O → H2) and an anodic Na+ de-intercalation reaction (Na0.44MnO2 → Na0.44-xMnO2), during which NaOH is produced in the electrolyte solution. The second step depends on a cathodic Na+ intercalation reaction (Na0.44-xMnO2 → Na0.44MnO2) and an anodic Cl2 production (Cl → Cl2). The cycle of the two steps provides a membrane-free process, which is potentially a promising direction for developing clean chlor-alkali technology.

TiP2O7 and Expanded Graphite Nanocomposite as Anode Material for Aqueous Lithium-Ion Batteries.

This paper reports a facile sol-gel synthesis method to successfully prepare the TiP2O7/expanded graphite (EG) nanocomposite as an advanced anode material for aqueous lithium-ion batteries. The constructed TiP2O7 nanocomposites (50-100 nm) are in situ encapsulated in the pore and layer structure of expanded graphite with good conductivity and high specific surface area. As a consequence, the resulting TiP2O7/EG electrode exhibits a reversible capacity of 66 mAh g-1 at 0.1 A g-1 with an appropriate potential of -0.6 V before hydrogen evolution in aqueous electrolytes, and also demonstrates greatly enhanced cycling stability with 75% capacity retention after 1000 cycles at the current density of 0.5 A g-1. A full cell consisting of TiP2O7/EG anode, LiMn2O4 cathode, and 1 M Li2SO4 electrolyte delivers a specific energy of 60 Wh kg-1 calculated on the weight of both cathode and anode materials with an operational voltage of 1.4 V. It also exhibits superior rate capability and remarkable cycling performance with a capacity maintenance of 66% over 500 cycles at 0.2 A g-1 and 61% at 1 A g-1 over 2000 cycles.