Ferroelectric Interfaces for Dendrite Prevention in Zinc-Ion Batteries.

Aqueous rechargeable zinc-ion batteries (ZIBs) are increasingly recognized as promising energy storage systems for mini-grid and mini-off-grid applications due to their advantageous characteristics such as high safety, affordability, and considerable theoretical capacity. However, the long-term cycling performance of ZIBs is hampered by challenges including the uncontrolled dendrite formation, the passivation, and the occurrence of the hydrogen evolution reaction (HER) on the Zn anode. In this study, enhancing ZIB performance by implementing oxide material coatings on Zn metal, serving as a physical barrier at the electrode-electrolyte interfaces to mitigate dendrite growth and suppress the HER is concentrated. Specifically, the mechanisms through which the n-type semiconductor TiO2 coated Zn anode establishes ohmic contact with Zn, and the high-dielectric BaTiO3 (BTO) coated Zn anode fosters Maxwell-Wagner polarization with ferroelectric properties, significantly inhibiting dendrite growth and side reactions, thereby resulting in a highly stable Zn anode for efficient aqueous ZIBs is explored. This advanced BTO/Zn electrode demonstrates an extended lifespan of over 700 h compared to bare Zn and TiO2/Zn anodes. Additionally, full-cell aqueous ZIBs incorporating BTO/Zn//VO2 (B) batteries exhibit superior rate capabilities, high capacity, and sustained cycle life.

Planar Zn-Ion Microcapacitors with High-Capacity Activated Carbon Anode and VO2 (B) Cathode.

The downsizing of microscale energy storage devices plays a crucial role in powering modern emerging devices. Therefore, the scientific focus on developing high-performance microdevices, balancing energy density and power density, becomes essential. In this context, we explore an advanced Microplotter technique to fabricate hybrid planar Zn-ion microcapacitors (ZIMCs) that exhibit dual charge storage characteristics, with an electrical double layer capacitor type activated carbon anode and a battery type VO2 (B) cathode, aiming to achieve energy density surpassing supercapacitors and power density exceeding batteries. Effective loading of VO2 (B) cathode electrode materials combined with activated carbon anode onto confined planar microelectrodes not only provides reversible Zn2+ storage performance but also mitigates dendrite formation. This not only results in superior charge storage performance, including areal energies of 2.34 µWh/cm2 (at 74.76 µW/cm2) and 0.94 µWh/cm2 (at 753.12 µW/cm2), exceeding performance of zinc nanoparticle anode and activated carbon cathode based ZIMCs, but also ensures stable capacity retention of 87% even after 1000 cycles and free from any unwanted dendrites. Consequently, this approach is directed toward the development of high-performance ZIMCs by exploring high-capacity materials for efficient utilization on microelectrodes and achieving maximum possible capacities within the constraints of the limited device footprint.

Advanced Porous Gold-PANI Micro-Electrodes for High-Performance On-Chip Micro-Supercapacitors.

The downsizing of microscale energy storage devices is crucial for powering modern on-chip technologies by miniaturizing electronic components. Developing high-performance microscale energy devices, such as micro-supercapacitors, is essential through processing smart electrodes for on-chip structures. In this context, we introduce porous gold (Au) interdigitated electrodes (IDEs) as current collectors for micro-supercapacitors, using polyaniline as the active material. These porous Au IDE-based symmetric micro-supercapacitors (P-SMSCs) show a remarkable enhancement in charge storage performance, with a 187% increase in areal capacitance at 2.5 mA compared to conventional flat Au IDE-based devices, despite identical active material loading times. Our P-SMSCs achieve an areal capacitance of 60 mF/cm2, a peak areal energy density of 5.44 µWh/cm2, and an areal power of 2778 µW/cm2, surpassing most reported SMSCs. This study advances high-performance SMSCs by developing highly porous microscale planar current collectors, optimizing microelectrode use, and maximizing capacity within a compact footprint.

Photothermal Enhancement of Prussian Blue Cathodes for Li-Ion Batteries.

Photoenhanced batteries, where light improves the electrochemical performance of batteries, have gained much interest. Recent reports suggest that light-to-heat conversion can also play an important role. In this work, we study Prussian blue analogues (PBAs), which are known to have a high photothermal heating efficiency and can be used as cathodes for Li-ion batteries. PBAs were synthesized directly on a carbon collector electrode and tested under different thermally controlled conditions to show the effect of photothermal heating on battery performance. Our PBA electrodes reach temperatures that are 14% higher than reference electrodes using a blue LED, and a capacity enhancement of 38% was achieved at a current density of 1600 mA g-1. Additionally, these batteries show excellent cycling stability with a capacity retention of 96.6% in dark conditions and 94.8% in light over 100 cycles. Overall, this work shows new insights into the effects leading to improved battery performance in photobatteries.

Hydrogenated V2O5 with Improved Optical and Electrochemical Activities for Photo-Accelerated Lithium-Ion Batteries.

Solar power represents an abundant and readily available source of renewable energy. However, its intermittent nature necessitates external energy storage solutions, which can often be expensive, bulky, and associated with energy conversion losses. This study introduces the concept of a photo-accelerated battery that seamlessly integrates energy harvesting and storage functions within a single device. In this research, a novel approach for crafting photocathodes is presented using hydrogenated vanadium pentoxide (H:V2O5) nanofibers. This method enhances optical activity, electronic conductivity, and ion diffusion rates within photo-accelerated Li-ion batteries. This study findings reveal that H:V2O5 exhibits notable improvements in specific capacity under both dark and illuminated conditions. Furthermore, it demonstrates enhanced diffusion kinetics and charge storage performance when exposed to light, as compared to pristine counterparts. This strategy of defect engineering holds great promise for the development of high-performance photocathodes in future energy storage applications.

Dendrite-Free Zinc Anodes Enabled by Exploring Polar-Face-Rich 2D ZnO Interfacial Layers for Rechargeable Zn-Ion Batteries.

Zinc metal is a promising candidate for anodes in zinc-ion batteries (ZIBs), but its widespread implementation is hindered by dendrite growth in aqueous electrolytes. Dendrites lead to undesirable side reactions, such as hydrogen evolution, passivation, and corrosion, causing reduced capacity during prolonged cycling. In this study, an approach is explored to address this challenge by directly growing 1D zinc oxide (ZnO) nanorods (NRs) and 2D ZnO nanoflakes (NFs) on Zn anodes, forming artificial layers to enhance ZIB performance. The incorporation of ZnO on the anode offers both chemical and thermal stability and leverages its n-type semiconductor nature to facilitate the formation of ohmic contacts. This results in efficient electron transport during Zn ion plating and stripping processes. Consequently, the ZnO NFs-coated Zn anodes demonstrate significantly improved charge storage performance, achieving 348 mAh g-1 , as compared to ZnO NRs (250 mAh g-1 ) and pristine Zn (160 mAh g-1 ) anodes when evaluated in full cells with V2 O5 cathodes. One significant advantage of ZnO NFs lies in their highly polar surfaces, promoting strong interactions with water molecules and rendering them exceptionally hydrophilic. This characteristic enhances the ability of ZnO NFs to desolvate Zn2+ ions, leading to improved charge storage performance.

Interrogating the Light-Induced Charging Mechanism in Li-Ion Batteries Using Operando Optical Microscopy.

Photobatteries, batteries with a light-sensitive electrode, have recently been proposed as a way of simultaneously capturing and storing solar energy in a single device. Despite reports of photocharging with multiple different electrode materials, the overall mechanism of operation remains poorly understood. Here, we use operando optical reflection microscopy to investigate light-induced charging in LixV2O5 electrodes. We image the electrode, at the single-particle level, under three conditions: (a) with a closed circuit and light but no electronic power source (photocharging), (b) during galvanostatic cycling with light (photoenhanced), and (c) with heat but no light (thermal). We demonstrate that light can indeed drive lithiation changes in LixV2O5 while maintaining charge neutrality, possibly via a combination of faradaic and nonfaradaic effects taking place in individual particles. Our results provide an addition to the photobattery mechanistic model highlighting that both intercalation-based charging and lithium concentration polarization effects contribute to the increased photocharging capacity.

Porous Carbon Coated on Cadmium Sulfide-Decorated Zinc Oxide Nanorod Photocathodes for Photo-accelerated Zinc Ion Capacitors.

The development of devices with dual solar energy-harvesting and storage functionalities has recently gained significant traction for off-grid power supply. In their most compact embodiment, these devices rely on the same electrode to harvest and store energy; however, in this approach, the development of energy-efficient photoelectrodes with intrinsic characteristics of good optical and electrochemical activities remains challenging. Here, we propose photoelectrodes with a porous carbon coated on a zinc oxide-cadmium sulfide heterostructure as an energy-efficient photocathode for photo-accelerated zinc ion capacitors (Photo-ZICs). The Photo-ZICs harvest light energy and store charge simultaneously, resulting in efficient charge storage performance under illumination compared to dark conditions (∼99% capacity enhancement at 500 mA g-1 under illumination compared to dark conditions). The light absorption ability and charge separation efficiency achieved by the photocathodes meet the requirements for photo-ZIC applications. Moreover, Photo-ZICs display stable charge storage capacities over long-term cycling, that is, ∼1% capacity loss after 10,000 cycles.

Photo-Enhanced Magnesium-Ion Capacitors Using Photoactive Electrodes.

Off-grid power sources are becoming increasingly important for applications ranging from autonomous sensor networks to fighting energy poverty. Interactions of light with certain classes of battery and capacitor materials have recently gained attention to enhance the rate performance or to even charge energy storage devices directly with light. Interestingly, these devices have the potential to reduce the volume and cost of autonomous power sources. Here, a light-enhanced magnesium (Mg)-ion capacitor is shown. The latter is interesting because of the large natural abundance of Mg and its ability to operate in low cost and non-flammable aqueous electrolytes. Photoelectrodes using a combination of vanadium dioxide and reduced graphene oxide can achieve capacitance enhancements of up to 56% under light exposure alongside a 21% higher energy density of 20.5 mAh kg-1 .

Molybdenum Disulfide-Zinc Oxide Photocathodes for Photo-Rechargeable Zinc-Ion Batteries.

Systems for harvesting and storing solar energy have found practical applications ranging from solar farms to autonomous smart devices. Generally, these energy solutions consist of solar cells for light harvesting and rechargeable batteries to match the solar energy supply to consumption demands. Rather than having a separate energy harvesting and storing device, we report photo-rechargeable zinc-ion batteries (hν-ZIBs) using a photoactive cathode composed of layer-by-layer grown zinc oxide and molybdenum disulfide. These photocathodes are capable of harvesting solar energy and storing it in the same material and alleviate the need for solar cells or power converters. The proposed photocathodes achieve photoconversion efficiencies of ∼1.8% using a 455 nm light source and ∼0.2% of solar-conversion efficiencies. Light not only allows photocharging but also enhances the battery capacity from 245 to 340 mA h g-1 (specific current of 100 mA g-1 and 12 mW cm-2 light intensity at 455 nm). Finally, the proposed hν-ZIBs also demonstrate a capacity retention of ∼82% over 200 cycles.

Light Rechargeable Lithium-Ion Batteries Using V2O5 Cathodes.

Solar energy is one of the most actively pursued renewable energy sources, but like many other sustainable energy sources, its intermittent character means solar cells have to be connected to an energy storage system to balance production and demand. To improve the efficiency of this energy conversion and storage process, photobatteries have recently been proposed where one of the battery electrodes is made from a photoactive material that can directly be charged by light without using solar cells. Here, we present photorechargeable lithium-ion batteries (Photo-LIBs) using photocathodes based on vanadium pentoxide nanofibers mixed with P3HT and rGO additives. These photocathodes support the photocharge separation and transportation process needed to recharge. The proposed Photo-LIBs show capacity enhancements of more than 57% under illumination and can be charged to ∼2.82 V using light and achieve conversion efficiencies of ∼2.6% for 455 nm illumination and ∼0.22% for 1 sun illumination.

Photo-Rechargeable Zinc-Ion Capacitor Using 2D Graphitic Carbon Nitride.

Off-grid energy storage devices are becoming increasingly important to power distributed applications, such as the Internet of things, and smart city ubiquitous sensor systems. To date, this has been achieved by combining an energy storage device, e.g., a battery or capacitor with an energy harvester, e.g., a solar cell. However, this approach inherently increases the device footprint and the output voltages of energy harvesters often do not match those required by energy storage device. Here we propose the first photo-rechargeable zinc-ion capacitors, where graphitic carbon nitride acts simultaneously as the capacitor electrode and light harvesting material. This approach allows light to be used to recharge the capacitor directly and they can be operated in a continuous light powered mode. These capacitors show a photo-rechargeable specific capacitance of ∼11377 mF g-1, a photo-charging voltage response of ∼850 mV, and a cyclability with ∼90% capacitance retention over 1000 cycles.

Flexible Array of Microsupercapacitor for Additive Energy Storage Performance Over a Large Area.

An on-chip microsupercapacitor (MSC) pattern is obtained by layer-by-layer spray deposition of both manganese dioxide (MnO2) nanoparticle-coated carbon nanotubes (MnO2-CNTs) and MnO2 nanosheet-decorated reduced graphene oxide (MnO2-rGO) on mechanically robust, flexible polyethylene terephthalate. Layer-by-layer patterning of MSC electrodes offers rapid in-plane diffusion of electrolyte ions in electrodes the layered electrode and hence ultrahigh capacitance and energy density of 7.43 mF/cm2 (32300 mF/cm3) and 0.66 µW h/cm2 (2870 µW h/cm3), respectively, are obtained. A robust electrochemical response was measured under multiple bending of the solid-state flexible MSC as well as under repetitive cycles (∼5000).

Surface photo-charge effect in doped-ZnO nanorods for high-performance self-powered ultraviolet photodetectors.

The unique photo-charge characteristics of chlorine-doped zinc oxide nanorods (Cl-ZnO NRs) are explored for the first time in ultraviolet (UV) photodetector (PD) that offers an outstanding self-powered photoresponse towards low UV illumination signals. A self-powered Cl-ZnO NRs PD exhibits superior photon detection speed of the order of a few ms with high sensitivity and photoelasticity. Therefore, the presented PD opens up a novel route to fabricate highly efficient self-powered PDs on a large scale without employing complex multilayer systems.

Conjugated assembly of colloidal zinc oxide quantum dots and multiwalled carbon nanotubes for an excellent photosensitive ultraviolet photodetector.

Conjugation of highly dense colloidal zinc oxide quantum dots (ZnO QDs) on multiwalled carbon nanotubes (ZnO QDs@MWCNTs) is achieved for high performance ultraviolet (UV) photodetection. Significant improvement in the photoresponse of the ZnO QDs@MWCNTs photodetector (PD) is established as compared to a pristine ZnO QDs PD. The conjugation of two constituents allows the direct transfer of photoinduced charge carriers in ZnO QDs to MWCNTs for an efficient electrical path that considerably reduces charge recombination during UV exposure. Linearity in the response current with both the UV illumination intensity as well as external bias voltage reveals the photoelastic behavior of the ZnO QDs@MWCNTs PD. Moreover, the PD displays faster response and recovery times of 1.6 s and 1.9 s, respectively, than the most conventional PDs. In addition, spectral photoresponse analysis of the PD presents visible-blind behavior. Overall, conjugation of the hybrid heterostructure presented excellent photoelastic, high performance and visible-blind UV photodetection.

Sandwiched assembly of ZnO nanowires between graphene layers for a self-powered and fast responsive ultraviolet photodetector.

A heterostructure of graphene and zinc oxide (ZnO) nanowires (NWs) is fabricated by sandwiching an array of ZnO NWs between two graphene layers for an ultraviolet (UV) photodetector. This unique structure allows NWs to be in direct contact with the graphene layers, minimizing the effect of the substrate or metal electrodes. In this device, graphene layers act as highly conducting electrodes with a high mobility of the generated charge carriers. An excellent sensitivity is demonstrated towards UV illumination, with a reversible photoresponse even for a short period of UV illumination. Response and recovery times of a few milliseconds demonstrated a much faster photoresponse than most of the conventional ZnO nanostructure-based photodetectors. It is shown that the generation of a built-in electric field between the interface of graphene and ZnO NWs effectively contributes to the separation of photogenerated electron-hole pairs for photocurrent generation without applying any external bias. Upon application of external bias voltage, the electric field further increases the drift velocity of photogenerated electrons by reducing the charge recombination rates, and results in an enhancement of the photocurrent. Therefore, the graphene-based heterostructure (G/ZnO NW/G) opens avenues to constructing a novel heterostructure with a combination of two functionally dissimilar materials.

Effect of Magnetic Field on Photoresponse of Cobalt Integrated Zinc Oxide Nanorods.

Cobalt integrated zinc oxide nanorod (Co-ZnO NR) array is presented as a novel heterostructure for ultraviolet (UV) photodetector (PD). Defect states in Co-ZnO NRs surface induces an enhancement in photocurrent as compared to pristine ZnO NRs PD. Presented Co-ZnO NRs PD is highly sensitive to external magnetic field that demonstrated 185.7% enhancement in response current. It is concluded that the opposite polarizations of electron and holes in the presence of external magnetic field contribute to effective separation of electron-hole pairs that have drifted upon UV illumination. Moreover, Co-ZnO NRs PD shows a faster photodetection speed (1.2 s response time and 7.4 s recovery time) as compared to the pristine ZnO NRs where the response and recovery times are observed as 38 and 195 s, respectively.

Few-layer graphene/ZnO nanowires based high performance UV photodetector.

A graphene and zinc oxide nanowires (G/ZnO NWs) based ultraviolet (UV) photodetector presents excellent responsivity and photocurrent gain with detectivity. Graphene due to higher charge carrier transport mobility induces faster response to UV illumination at the interface between ZnO and graphene with improved response and decay times as compared to a ZnO NWs device alone. A linear increase is revealed for both the responsivity and photocurrent gain of the G/ZnO NWs device with the applied bias. These results suggest that the G/ZnO NWs device exhibits great promise for highly efficient UV photodetectors.

Highly Dense ZnO Nanowires Grown on Graphene Foam for Ultraviolet Photodetection.

Growth of highly dense ZnO nanowires (ZnO NWs) is demonstrated on three-dimensional graphene foam (GF) using resistive thermal evaporation technique. Photoresponse of the as-grown hybrid structure of ZnO NWs on GF (ZnO NWs/GF) is evaluated for ultraviolet (UV) detection. Excellent photoresponse with fast response and recovery times of 9.5 and 38 s with external quantum efficiency of 2490.8% is demonstrated at low illumination power density of 1.3 mW/cm(2). In addition, due to excellent charge carrier transport, mobility of graphene reduces the recombination rate of photogenerated charge carriers, hence the lifetime of photogenerated free charge carriers enhances in the photodetectors.