Flexible Supercapacitor with Wide Electrochemical Stable Window Based on Hydrogel Electrolyte.

Hydrogel electrolyte can endow supercapacitors with excellent flexibility, which has developed rapidly in recent years. However, the water-rich structures of hydrogel electrolyte are easy to freeze at subfreezing and dry at high temperatures, which will affect its energy storage characteristics. The low energy density of micro supercapacitors also hinders their development. Herein, a strategy is proposed to reduce the free water activity in the hydrogel to improve the operating voltage and the energy density of the device, which is achieved through the synergistic effect of the hydrogel skeleton, N, N'-dimethylformamide (DMF), NaClO4 and water. High concentrations of DMF and NaClO4 are introduced into sodium alginate/polyacrylamide (SA/PAAM) hydrogel through solvent exchange to obtain SA/PAAM/DMF/NaClO4 hydrogel electrolyte, which exhibited a high ionic conductivity of 82.1 mS cm-1, a high breaking strength of 563.2 kPa, and a wide voltage stability window of 3.5 V. The supercapacitor devices are assembled by the process of direct adhesion of the hydrogel electrolyte and  laser induced graphene (LIG). The micro-supercapacitor exhibited an operating voltage of 2.0 V, with a specific capacitance of 2.41 mF cm-2 and a high energy density of 1.34 µWh cm-2, and it also exhibit a high cycle stability, good flexibility, and integration performance.

Perspectives on Working Voltage of Aqueous Supercapacitors.

Aqueous supercapacitors have the superiorities of high safety, environmental friendliness, inexpensive, etc. High energy density supercapacitors are not conducive to manufacturing due to the limitation of water thermodynamic decomposition potential, resulting in a narrow working voltage window. To address such challenges, a great endeavor has started to investigate high voltage aqueous supercapacitors as well as making some progress. This review summarizes key strategies regarding the realization of wide working voltage of aqueous supercapacitors and analyzes the involved mechanism, including the optimization of electrodes, electrolytes, diaphragms, and supercapacitor structures. From the perspective of extending the theoretical voltage window, electrode functionalization, heteroatom doping, neutral electrolyte, water-in-salt electrolyte, introducing redox mediators into electrolyte, and designing asymmetric structure are effective strategies for achieving this goal. Further, the actual voltage window can be maximized by optimizing the electrode mass ratio, adjusting potential of zero voltage, and electrode functionalization. The challenge and future of expanding working voltage of aqueous supercapacitors are further discussed. Importantly, this review provides inspiration for the development of supercapacitors with high energy density.

Origins of Boosted Charge Storage on Heteroatom-Doped Carbons.

Although tremendous efforts have been devoted to understanding the origin of boosted charge storage on heteroatom-doped carbons, none of the present studies has shown a whole landscape. Herein, by both experimental evidence and theoretical simulation, it is demonstrated that heteroatom doping not only results in a broadened operating voltage, but also successfully promotes the specific capacitance in aqueous supercapacitors. In particular, the electrolyte cations adsorbed on heteroatom-doped carbon can effectively inhibit hydrogen evolution reaction, a key step of water decomposition during the charging process, which broadens the voltage window of aqueous electrolytes even beyond the thermodynamic limit of water (1.23 V). Furthermore, the reduced adsorption energy of heteroatom-doped carbon consequently leads to more stored cations on the heteroatom-doped carbon surface, thus yielding a boosted charge storage performance.

Origin of electrochemical voltage range and voltage profile of insertion electrodes.

This study evaluates electrochemical voltage-range and voltage-profile regarding electrodes of insertion (intercalation) batteries. The phrase "voltage-range" expresses the difference between obtained maximum and minimum potential for the cells. It also can be called as operating voltage-range, working voltage-range, electrochemical voltage-range, or voltage window. This paper proposes a new notion regarding electron density of states, i.e. trans-band, which can be implemented to justify the voltage -range and -profile, by means of Fermi levels' alignment. Voltage -range and -profile of a number of insertion electrode materials are clarified by the proposed theoretical approach, namely LiMn2O4, Li2Mn2O4, ZnMn2O4, LiFePO4, LiCoO2, Li2FeSiO4, LiFeSO4F, and TiS2. Moreover, the probable observed difference between charge and discharge profile is explained by the approach. The theoretical model/approach represents a number of important concepts, which can meet some scientific fields, e.g. electrochemistry, energy storage devices, solid state physics (DFT), and phase diagrams. By means of DFT calculations, this paper deals with quantizing the energy of electrochemical reactions, justifying the configuration of voltage-profile, and explaining the origin of the voltage-range. Accordance with the experimental observations suggests that this paper can extend boundary of quantum mechanics toward territories of classical thermodynamics, and boundary of the modern thermodynamics toward kinetics. Opening a new horizon in the related fields, this paper can help tuning, engineering, and predicting cell-voltage behavior.

Low Reducing Potentials Enabled by CaF2-Supported Graphene Electrodes in High Impedance Solutions.

We report electrochemical measurements using in situ Raman spectroscopy at graphene/D2O interfaces under extremely low applied potentials. Here, the hydrophobic and catalytically inert nature of graphene and the insulating nature of the deionized (DI) water enables potentials as low as Vapplied = -7 V vs Ag/AgCl to be applied without exceeding 200 µA/cm2 of current density. At higher currents, bubble formation (i.e., hydrogen evolution reaction) prohibits reliable spectra from being obtained from the electrode surface. Using CaF2 as the supporting substrate enables significantly lower reducing potentials to be reached compared to glass substrates, likely due to trapped charge and impurities in the glass substrate. G band Raman spectra taken under various applied electrochemical potentials exhibit a linear relationship between the G band shift (ΔωG) and the applied potential, with blueshifts as high as ΔωG = 18 cm-1. These large Raman shifts indicate a large change in the Fermi level of ΔEF = -0.43 eV for graphene electrodes in contact with water, favoring reduction half-reactions. Based on the solution resistance measurement, there is a VIR = 3.1 V voltage drop across the solution for D2O (when the applied potential was Vapplied = -7 V vs Ag/AgCl) and the effective reducing potential on the working electrode is Veffective = -3.9 V vs Ag/AgCl. We have also tested these graphene electrodes in ionic liquids [DEME][TFSI], which are limited to applied potentials above Vapplied = -2.7 V vs Ag/AgCl and a corresponding shift in the Fermi level ΔEF = -0.32 eV, indicating that pure water can provide a more robust electrolyte for reaching low reducing potentials than ionic liquids.

Different metal cation-doped MnO2/carbon cloth for wide voltage energy storage.

Aqueous gel supercapacitors, as an important component of flexible energy storage devices, have received widespread attention for their fast charging/discharging rates, long cycle life and high electrochemical stability under mechanical deformation condition. However, the low energy density of aqueous gel supercapacitors has greatly hindered their further development due to the narrow electrochemical window and limited energy storage capacity. Therefore, different metal cation-doped MnO2/carbon cloth-based flexible electrodes herein are prepared by constant voltage deposition and electrochemical oxidation in various saturated sulphate solutions. The influence of different metal cations as K+, Na+ and Li+ doping and deposition conditions on the apparent morphology, lattice structure and electrochemical properties are explored. Furthermore, the pseudo-capacitance ratio of the doped MnO2 and the voltage expansion mechanism of the composite electrode are investigated. The specific capacitance and pseudo-capacitance ratio of the optimized δ-Na0.31MnO2/carbon cloth as MNC-2 electrode could be reached 327.55 F/g at 10 mV/s and 35.56% of the pseudo-capacitance, respectively. The flexible symmetric supercapacitors (NSCs) with desirable electrochemical performances in the operating range of 0-1.4 V are further assembled with MNC-2 as the electrodes. The energy density is 26.8 Wh/kg at the power density of 300 W/kg, while the energy density can still reach 19.1 Wh/kg when the power density is up to 1150 W/kg. The energy storage devices with high-performance developed in this work can provide new ideas and strategic support for the application in portable and wearable electronic devices.

Efficient pH-universal aqueous supercapacitors enabled by an azure C-decorated N-doped graphene aerogel.

Current aqueous supercapacitors (SCs) possess the relative low energy density, and there is therefore widespread interest in cost-effective fabrication of capacitive materials with promoted specific capacitance and/or broadened voltage window. Here, a redox-active azure C-decorated N-doped graphene aerogel (AC - NGA) is fabricated using a simple hydrothermal self-assembly method through strong noncovalent π-π interaction. AC - NGA highlights an excellent charge storage performance (a high 591F g-1 gravimetric capacitance under a current density of 1.0 A g-1 and ultrahigh voltage window of 2.3 V) under pH-universal conditions. The capacitive contribution of charge storage is 91.7%, exceeding or comparable to those of the best pseudocapacitors known. Furthermore, a symmetric AC - NGA//AC - NGA device realizes high energy and power densities (15.2-60.2 Wh kg-1 at 650-23,000 W kg-1) and excellent cycling stability in acidic, neutral, and basic aqueous solutions. This work offers a cost-effective strategy to combine redox dye molecules with heteroatom-doped graphene aerogel for building green efficient pH-universal aqueous supercapacitors.

Versatile potassium vanadium fluorophosphate (KVPO4F) composites as Dual-Function cathode and anode materials for Potassium-Ion hybrid capacitors.

Potassium-based energy storage has emerged as a promising alternative for advanced energy storage systems, driven by the abundance of potassium, fast ion migration, and low standard electrode potential. Hybrid capacitors, which combine the desirable characteristics of batteries and supercapacitors, offer a compelling solution for efficient energy storage. In this study, we present the development of versatile composite materials, specifically potassium vanadium fluorophosphate (KVPO4F) composites, utilizing a sol-gel method. These composites enable tunable potassium storage and charge transport kinetics within regulated voltage windows, serving as both cathode and anode materials. The anode composite, composed of KVPO4F and hierarchical porous carbon (HPC), exhibited exceptional stability over 400 cycles within a low-voltage window. On the other hand, the cathode composite, consisting of battery-like KVPO4F and physisorption activated carbon (AC), demonstrated great potential as a cathode material, striking a balance between specific energy and cycle life within a regulated high-voltage window. By integrating KVPO4F/C as the anode and KVPO4F/AC as the cathode, we successfully created potassium-ion hybrid capacitors (PIHCs) that showcased an impressive capacity retention of 83% after 10,000 cycles within a high voltage window of 0.5-4.3 V. Furthermore, to explore the application of these materials in miniaturized energy storage, we fabricated potassium-ion micro hybrid capacitors (PIMHCs) with interdigitated electrodes. These devices exhibited a high areal energy density of 18.8 µWh cm-2 at a power density of 111.6 µW cm-2, indicating their potential for compact energy storage systems. The results of this study demonstrate the versatility and efficacy of the developed KVPO4F composite materials, highlighting their potential for future advancements in potassium-based energy storage technologies.

Ultra-Low-Power and Wide-Operating-Voltage-Window Capacitive Piezotronic Sensor through Coupling of Piezocharges and Depletion Widths for Tactile Sensing.

The rapid growth of Artificial Intelligence and Internet of Things (AIoT) demands the development of ultra-low-power devices for future advanced technology. In this study, we introduce a capacitive piezotronic sensor specifically designed for tactile sensing, which enables an ultra-low-voltage operation at nearly 0 reading bias conditions with a consistent response within a wide voltage range. This sensor directly detects capacitance changes induced by piezocharges, reflecting perturbation of the effective depletion width, and ensures ultralow power capability by eliminating the necessity of turning on the Schottky diode for the first time. The dynamic response of the sensor demonstrates ultralow power capability and immunity to triboelectric interference, making it particularly suitable for tactile sensing applications in robotics, prosthetics, and wearables. This study provides valuable insights and design guidelines for future ultra-low-power thin-film-based capacitive piezotronic/piezophototronic devices for tactile sensing.

In-situ preparation of amorphous VO2@rGO cathode for ultra-high capacity and ultra-long cycle life aqueous zinc ion batteries.

Aqueous zinc-ion batteries (AZIBs) are considered as a promising alternative to lithium-ion batteries for stationary energy storage due to their environmental benignity and cost-effectiveness. However, the development of AZIBs continues to be plagued by a lack of cathode materials with high specific capacity and superior lifetime. Herein, we in-situ synthesize amorphous VO2@rGO assisted by controlling the charging cut-off voltage. Experimental results and theoretical calculations confirm that the amorphous VO2(A)@rGO can effectively reduce the migration energy barrier of Zn2+, improve the conductivity of the electrode, and promote the insertion/extraction of Zn2+. Consequently, the Zn//VO2(A)@rGO battery exhibits an ultra-high specific capacity of 527.0 mAh·g-1 at 1 A·g-1 after 100 cycles, an ultra-long cycle stability of 183.4 mAh·g-1 at 20 A·g-1 after 30,000 cycles, and an energy of 316.1 Wh·Kg-1 at a power density of 6082.9 W·Kg-1 power density. Meanwhile, we reveal that the amorphous VO2@rGO electrode follows a hybrid mechanism of classical Zn2+ insertion/de-insertion and the reversible phase transition from amorphous VO2 to V2O3. This study highlights that in-situ preparation of amorphous VO2@rGO cathode materials by controlling the charging voltage interval, opening up further possibilities for the development of high-performance AZIB cathodes.

Rational Design of Ni-Doped V2O5@3D Ni Core/Shell Composites for High-Voltage and High-Rate Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries (ZIBs) have significant potential for large energy storage systems because of their high energy density, cost-effectiveness and environmental friendliness. However, the limited voltage window, poor reaction kinetics and structural instability of cathode materials are current bottlenecks which contain the further development of ZIBs. In this work, we rationally design a Ni-doped V2O5@3D Ni core/shell composite on a carbon cloth electrode (Ni-V2O5@3D Ni@CC) by growing Ni-V2O5 on free-standing 3D Ni metal nanonets for high-voltage and high-capacity ZIBs. Impressively, embedded Ni doping increases the interlayer spacing of V2O5, extending the working voltage and improving the zinc-ion (Zn302+) reaction kinetics of the cathode materials; at the same time, the 3D structure, with its high specific surface area and superior electronic conductivity, aids in fast Zn302+ transport. Consequently, the as-designed Ni-V2O5@3D Ni@CC cathodes can operate within a wide voltage window from 0.3 to 1.8 V vs. Zn30/Zn302+ and deliver a high capacity of 270 mAh g-1 (~1050 mAh cm-3) at a high current density of 0.8 A g-1. In addition, reversible Zn2+ (de)incorporation reaction mechanisms in the Ni-V2O5@3D Ni@CC cathodes are investigated through multiple characterization methods (SEM, TEM, XRD, XPS, etc.). As a result, we achieved significant progress toward practical applications of ZIBs.

Hydrogen Bond Interaction in the Trade-Off Between Electrolyte Voltage Window and Supercapacitor Low-Temperature Performances.

Liquid electrolyte determines the voltage window and extreme working temperature of supercapacitors. However, the effect of weak interaction between electrolyte species on voltage window and low-temperature capacitive performance is unclear. Herein, an electrolyte model system with increasing H-bond interaction was constructed to clarify this concern. The results indicated that strong H-bond interaction was positively correlated with the number of hydroxyls, which was beneficial to expand voltage window, but deteriorated rate performance; weak H-bond improved low-temperature performance. Supercapacitors with an optimized electrolyte presented high voltage and good low-temperature performance; even at -40 °C, the maximum energy density could be maintained at 7.0 Wh kg-1 (>80 % retention relative to at -20 °C). This study revealed the mechanism of the influence of the H-bonds on electrolyte voltage window and anti-freezing capability and provided a new insight for the design of electrolytes with both high working voltage and low-temperature performance.

Design of Boron Carbonitrides-Polyaniline (BCN-PANI) assembled supercapacitor with high voltage window.

Boron carbonitrides (BCN) have been widely concerned in the field of energy storage and conversion. However, the energy storage mechanism of electrical double-layer behavior and their stacked-layer structure severely limit the improvement of capacitance, thereby hindering their further development in energy storage. Therefore, an ultrasonic-ball milling method was first chosen to obtain BCN nanosheets, together with a feasible way of polyaniline (PANI) modification performed to boost the capacitive reaction of BCN nanosheets. For the first time, a BCN-PANI-based symmetric supercapacitor device can reach a high voltage window of 3.0 V when 1 M Et4N·BF4 was chosen as the electrolyte. The working voltage of 3.0 V is three times that of a device with pure PANI with the ultrahigh energy density of 67.1 W h kg-1, superior to most of the reported PANI-based devices. The eminent electrochemical performance provides a promising strategy to pave the way for configuring carbon-based multiple composite electrodes for other energy storage devices.

High-Performance-Integrated Stretchable Supercapacitors Based on a Polyurethane Organo/Hydrogel Electrolyte.

Stretchable supercapacitors (SSCs) are promising energy storage devices for emerging wearable electronics. However, the low-energy density and poor deformation performance are still a challenge. Herein, an amphiphilic polyurethane-based organo/hydrogel electrolyte (APUGE) with a H2O/AN-in-salt (H2O/AN-NaClO4) is prepared for the first time. The as-prepared APUGE shows a wide voltage window (∼2.3 V), good adhesion, and excellent resilience. In addition, the intrinsically stretchable electrodes are prepared by coating the activated carbon slurry onto the PU/carbon black/MWCNT conductive elastic substrate. Based on the strong interface adhesion of the PU matrix, the as-assembled SSC delivers high-energy density (5.65 mW h cm-3 when the power density is 0.0256 W cm-3) and excellent deformation stability with 94.5% capacitance retention after 500 stretching cycles at 100% strain. This fully integrated construction concept is expected to be extended to multisystem stretchable metal ion batteries, stretchable lithium-sulfur batteries, and other stretchable energy storage devices.

Diamond Supercapacitors: Towards Durable, Safe, and Biocompatible Aqueous-Based Energy Storage.

Durable and safe energy storage is required for the next generation of miniature bioelectronic devices, in which aqueous electrolytes are preferred due to the advantages in safety, low cost, and high conductivity. While rechargeable aqueous batteries are among the primary choices with relatively low power requirements, their lifetime is generally limited to a few thousand charging/discharging cycles as the electrode material can degrade due to electrochemical reactions. Electrical double layer capacitors (EDLCs) possess increased cycling stability and power density, although with as-yet lower energy density, due to quick electrical adsorption and desorption of ions without involving chemical reactions. However, in aqueous solution, chemical reactions which cause electrode degradation and produce hazardous species can occur when the voltage is increased beyond its operation window to improve the energy density. Diamond is a durable and biocompatible electrode material for supercapacitors, while at the same time provides a larger voltage window in biological environments. For applications requiring higher energy density, diamond-based pseudocapacitors (PCs) have also been developed, which combine EDLCs with fast electrochemical reactions. Here we inspect the properties of diamond-related materials and discuss their advantages and disadvantages when used as EDLC and PC materials. We argue that further optimization of the diamond surface chemistry and morphology, guided by computational modelling of the interface, can lead to supercapacitors with enhanced performance. We envisage that such diamond-based supercapacitors could be used in a wide range of applications and in particular those requiring high performance in biomedical applications.

Optimal Energetic-Trap Distribution of Nano-Scaled Charge Trap Nitride for Wider Vth Window in 3D NAND Flash Using a Machine-Learning Method.

A machine-learning (ML) technique was used to optimize the energetic-trap distributions of nano-scaled charge trap nitride (CTN) in 3D NAND Flash to widen the threshold voltage (Vth) window, which is crucial for NAND operation. The energetic-trap distribution is a critical material property of the CTN that affects the Vth window between the erase and program Vth. An artificial neural network (ANN) was used to model the relationship between the energetic-trap distributions as an input parameter and the Vth window as an output parameter. A well-trained ANN was used with the gradient-descent method to determine the specific inputs that maximize the outputs. The trap densities (NTD and NTA) and their standard deviations (σTD and σTA) were found to most strongly impact the Vth window. As they increased, the Vth window increased because of the availability of a larger number of trap sites. Finally, when the ML-optimized energetic-trap distributions were simulated, the Vth window increased by 49% compared with the experimental value under the same bias condition. Therefore, the developed ML technique can be applied to optimize cell transistor processes by determining the material properties of the CTN in 3D NAND Flash.

Fluorinated Carbons as Rechargeable Li-Ion Battery Cathodes in the Voltage Window of 0.5-4.8 V.

Fluorinated carbon (CFx) cathodes have the highest theoretical energy density among lithium primary batteries. However, it is still a huge challenge to be reversible. Here, CFx is proposed as a high-performance cathode material for rechargeable lithium-ion batteries in the extended voltage window of 0.5-4.8 V. Specifically, the fluorinated graphite CF0.88 exhibits an initial specific discharge capacity of 1382 mAh g-1 (2362 Wh kg-1) and a specific discharge capacity of 782 mAh g-1 at the 2nd cycle and maintains a specific discharge capacity of 543 mAh g-1 (508 Wh kg-1) after the 20th cycle. This rechargeable behavior is associated with the conversion of CFx to LiF + C (>1.5 V) and then to Li1+xFC (0.5-1.5 V) during the initial discharge process; Li1+xFC is reversible to LiF + C in the following charge-discharge process (0.5-4.8 V). By extending the voltage window, CFx cathodes can show new electrochemical behaviors. Our research has provided new Li-free cathode materials for rechargeable batteries and insights for improving the performance of a Li/CFx secondary battery.

Narrowing Working Voltage Window to Improve Layered GeP Anode Cycling Performance for Lithium-Ion Batteries.

Layered germanium phosphide (GeP), a recently developed two-dimensional material, promises highly attractive theoretical capacity for use as a lithium-ion battery anode. Here, we comprehensively investigate its electrochemical performance and the modification mechanism. GeP flakes demonstrate large initial discharge/charge capacity and high initial Coulombic efficiency. However, the cycling performance is disappointing in the potential window of 0.001-3 V in which capacity retention is only ∼18% after 100 cycles. In situ transmission electron microscopy reveals that the poor cycling behavior results in the unexpected large volume change induced by complex reaction processes in cycles. Serious cracking and fracture appear clearly on the electrode surface after cycling. Narrowing the working voltage window to 0.001-0.85 V, cycling stability will be greatly enhanced, with 75% capacity retaining after 100 cycles and ∼50% left after 350 cycles due to the absence of the dealloying of Li3P in the narrowed working voltage window. Additionally, the electric contact among the electrode components has been enhanced by the alleviation of the electrode volume change in the narrowed working voltage window. Our work provides one effective method to give a deep understanding of the high-energy-density electrode failure and helps to narrow the huge gap between the microstructure and the performance of the electrode.

CNT/High Mass Loading MnO2/Graphene-Grafted Carbon Cloth Electrodes for High-Energy Asymmetric Supercapacitors.

Flexible supercapacitor electrodes with high mass loading are crucial for obtaining favorable electrochemical performance but still challenging due to sluggish electron and ion transport. Herein, rationally designed CNT/MnO2/graphene-grafted carbon cloth electrodes are prepared by a "graft-deposit-coat" strategy. Due to the large surface area and good conductivity, graphene grafted on carbon cloth offers additional surface areas for the uniform deposition of MnO2 (9.1 mg cm-2) and facilitates charge transfer. Meanwhile, the nanostructured MnO2 provides abundant electroactive sites and short ion transport distance, and CNT coated on MnO2 acts as interconnected conductive "highways" to accelerate the electron transport, significantly improving redox reaction kinetics. Benefiting from high mass loading of electroactive materials, favorable conductivity, and a porous structure, the electrode achieves large areal capacitances without compromising rate capability. The assembled asymmetric supercapacitor demonstrates a wide working voltage (2.2 V) and high energy density of 10.18 mWh cm-3.

TiN Paper for Ultrafast-Charging Supercapacitors.

Ultrafast-charging energy storage devices are attractive for powering personal electronics and electric vehicles. Most ultrafast-charging devices are made of carbonaceous materials such as chemically converted graphene and carbon nanotubes. Yet, their relatively low electrical conductivity may restrict their performance at ultrahigh charging rate. Here, we report the fabrication of a porous titanium nitride (TiN) paper as an alternative electrode material for ultrafast-charging devices. The TiN paper shows an excellent conductivity of 3.67 × 104 S m-1, which is considerably higher than most carbon-based electrodes. The paper-like structure also contains a combination of large pores between interconnected nanobelts and mesopores within the nanobelts. This unique electrode enables fast charging by simultaneously providing efficient ion diffusion and electron transport. The supercapacitors (SCs) made of TiN paper enable charging/discharging at an ultrahigh scan rate of 100 V s-1 in a wide voltage window of 1.5 V in Na2SO4 neutral electrolyte. It has an outstanding response time with a characteristic time constant of 4 ms. Significantly, the TiN paper-based SCs also show zero capacitance loss after 200,000 cycles, which is much better than the stability performance reported for other metal nitride SCs. Furthermore, the device shows great promise in scalability. The filtration method enables good control of the thickness and mass loading of TiN electrodes and devices.