Mechanistic Understanding of the Underlying Energy Storage Mechanism of α-MnO2-based Pseudo-Supercapacitors.

Manganese dioxide (α-MnO2) has attracted significant research interest in supercapacitors recently. However, the reaction mechanism of α-MnO2 in supercapacitors remains unclear. Therefore, a nano-supercapacitor using Environmental transmission electron microscopy (ETEM) is conducted and investigated the reaction mechanism of α-MnO2 based on three ionic liquids (ILs). It found that in the aprotic ionic liquid (AIL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMIMOTF), α-MnO2 nanowires (NWs) undergo an oxidation reaction due to the presence of an active proton at the second position (H2) of the imidazole ring. As a result, α-MnO2 NWs undergo a phase transition and transform into Mn3O4, exhibiting pseudo-capacitive properties. Furthermore, characterization of the macroscopic α-MnO2 electrodes after cycling reveals that after the initial charging cycles, the dominant energy storage mechanism of the supercapacitor transitions from pseudo-capacitance to a dual-layer capacitance formed by the combination of Mn3O4 and unreacted α-MnO2. Simultaneously, due to the coexistence of these two energy storage mechanisms, the specific capacitance of the supercapacitor in EMIMOTF electrolyte reaches up to 80 F g-1, and the cycle number reaches as high as 1000 cycles. The results are expected to provide insights into the selection of electrolytes in supercapacitors and offer a fundamental understanding of the internal reaction mechanisms in capacitors.

Boosting of Redox-Active Polyimide Porous Organic Polymers with Multi-Walled Carbon Nanotubes towards Pseudocapacitive Energy Storage.

Redox-active porous organic polymers (POPs) demonstrate significant potential in supercapacitors. However, their intrinsic low electrical conductivity and stacking tendencies often lead to low utilization rates of redox-active sites within their structural units. Herein, polyimide POPs (donated as PMTA) are synthesized in situ on multi-walled carbon nanotubes (MWCNTs) from tetramino-benzoquinone (TABQ) and 1,4,5,8-naphthalene tetracarboxylic dianhydride (PMDA) monomers. The strong π-π stacking interactions drive the PMTA POPs and the MWCNTs together to form a PMTA/MWCNT composite. With the assistance of MWCNTs, the stacking issue and low conductivity of PMTA POPs are well addressed, leading to the obvious activation and enhanced utilization of the redox-active groups in the PMTA POPs. PMTA/MWCNT then achieves a high capacitance of 375.2 F g-1 at 1 A g-1 as compared to the pristine PMTA POPs (5.7 F g-1) and excellent cycling stability of 89.7% after 8000 cycles at 5 A g-1. Cyclic voltammetry (CV) and in situ Fourier-Transform Infrared (FT-IR) results reveal that the electrode reactions involve the reversible structural evolution of carbonyl groups, which are activated to provide rich pseudocapacitance. Asymmetric supercapacitors (ASCs) assembled with PMTA/MWCNTs and activated carbon (AC) offer a high energy density of 15.4 Wh kg-1 at 980.4 W kg-1 and maintain a capacitance retention of 125% after 10,000 cycles at 5 A g-1, indicating their good potential for practical applications.

Engineering Mn Vacancies to Enhance Ion Kinetics in Layered Manganese Silicate for High-Energy and Durable Intercalation Pseudocapacitance.

Transition metal silicates (TMSs) are potential electrodes for aqueous metal-ion intercalation pseudocapacitors owing to their superior theoretical capacity and high structural stability. However, the narrow interlayer spacing and intrinsic inert basal plane of TMSs lead to sluggish ions and charge transfer, causing an undesirable energy storage performance. Herein, rich Mn vacancies are introduced in layered manganous silicates (M2-xS@FA) to expedite K+ diffusion, while enhancing charge storage capacity and prolonging lifespan. In situ characterizations validate the K+ intercalation pseudocapacitance mechanism with evident crystal structure and valence state variations in M2-xS@FA. Both theoretical calculations and electrochemical experimental evaluations elucidate the imperative role of Mn vacancies in enhancing K+ diffusion kinetics and electron transfer through increased interlayer spacing and activated basal plane. Mn vacancies further boost the charge storage capacity by providing additional K+ storage sites, while simultaneously reinforcing local atomic bonding within M2-xS@FA, thereby augmenting structural stability. The assembled aqueous asymmetric solid-state cell, featuring a M2-xS@FA cathode, demonstrates exceptional power and energy densities (144.08 W h kg-1 at 375.80 W kg-1) and ultralong lifespan (100% capacity retention after 10,000 cycles). This work heralds a paradigm whereby modulating cation vacancies in layered TMSs significantly enhances K+ storage and stability for high-energy intercalation pseudocapacitance.

Revisiting the Electrochemical Impedance Spectroscopy of Porous Electrodes in Li-ion Batteries by Employing Reference Electrode.

Electrochemical impedance spectroscopy (EIS), characterized by its non-destructive and in situ nature, plays a crucial role in comprehending the thermodynamic and kinetic processes occurring within Li-ion batteries. However, there is a lack of consistent and coherent physical interpretations for the EIS of porous electrodes. Therefore, it is imperative to conduct thorough investigations into the underlying physical mechanisms of EIS. Herein, by employing reference electrode in batteries, we revisit the associated physical interpretation of EIS at different frequencies. Combining different battery configurations, temperature-dependent experiments, and elaborated distribution of relaxation time analysis, we find that the ion transport in porous electrode channels and pseudo-capacitance behavior dominate the high-frequency and mid-frequency impedance arcs, respectively. This work offers a perspective for the physical interpretation of EIS and also sheds light on the understanding of EIS characteristics in other advanced energy storage systems.

Selective Capacitive Recovery of Rare-Earth Ions from Wastewater over Phosphorus-Modified TiO2 Cathodes via an Electro-Adsorption Process.

Large amounts of wastewater containing low-concentration (<10 ppm) rare-earth ions (REIs) are discharged annually in China's rare-earth mining and processing industry, resulting in severe environmental pollution and economic losses. Hence, achieving efficient selective recovery of low-concentration REIs from REIs-containing wastewater is essential for environmental protection and resource recovery. In this study, a pseudocapacitance system was designed for highly efficient capacitive selective recovery of REIs from wastewater using the titanium dioxide/P/C (TiO2/P/C) composite electrode, which exhibited over 99% recovery efficiency for REIs, such as Eu3+, Dy3+, Tb3+, and Lu3+ in mixed solution. This system maintained high efficiency and more than 90 times the enrichment concentration of REIs even after 100 cycles. Ti4+ of TiO2 was reduced to Ti3+ of Ti3O5 under forward voltage in the system, which trapped the electrons of phosphorus site and caused it to be oxidized to phosphate with a strong affinity for REIs, thus improving the selectivity of REIs. Under reverse voltage, Ti3O5 was oxidized to TiO2, which transferred electrons to phosphate and transformed to the phosphorus site, resulting in the desorption and enrichment of REIs and the regeneration of the electrode. This study provides a promising method for the efficient recovery of REIs from wastewater.

Elucidating High Initial Coulombic Efficiency, Pseudocapacitive Kinetics and Charge Storage Mechanism of Antiperovskite Carbide Ni3ZnC0.7@rGO Anode for Fast Sodium Storage in Ether Electrolyte.

To explore novel electrode materials with in-depth elucidation of initial coulombic efficiency (ICE), kinetics, and charge storage mechanisms is of great challenge for Na-ion storage. Herein, a novel 3D antiperovskite carbide Ni3ZnC0.7@rGO anode coupled with ether-based electrolyte is reported for fast Na-ion storage, exhibiting superior performance than ester-based electrolyte. Electrochemical tests and density functional theory (DFT) calculations show that Ni3ZnC0.7@rGO anode with ether-based electrolyte can promote charge/ion transport and lower Na+ diffusion energy barrier, thereby improving ICE, reversible capacity, rate, and cycling performance. Cross-sectional-morphology and depth profiling surface chemistry demonstrate that not only a thinner and more homogeneous reaction interface layer with less side effects but also a superior solid electrolyte interface (SEI) film with a high proportion of inorganic components are formed in the ether-based electrolyte, which accelerates Na+ transport and is the significant reason for the improvement of ICE and other electrochemical properties. Meanwhile, electrochemical and ex situ measurements have revealed conversion, alloying, and co-intercalation hybrid mechanisms of the Ni3ZnC0.7@rGO anode based on ether electrolyte. Interestingly, the Na-ion capacitors (SICs) designed by pairing with activated carbon (AC) cathode exhibit favorable electrochemical performance. Overall, this work provides deep insights on developing advanced materials for fast Na-ion storage.

A Highly Robust and Conducting Ultramicroporous 3D Fe(II)-Based Metal-Organic Framework for Efficient Energy Storage.

Exploitation of metal-organic framework (MOF) materials as active electrodes for energy storage or conversion is reasonably challenging owing to their poor robustness against various acidic/basic conditions and conventionally low electric conductivity. Keeping this in perspective, herein, a 3D ultramicroporous triazolate Fe-MOF (abbreviated as Fe-MET) is judiciously employed using cheap and commercially available starting materials. Fe-MET possesses ultra-stability against various chemical environments (pH-1 to pH-14 with varied organic solvents) and is highly electrically conductive (σ = 0.19 S m-1) in one fell swoop. By taking advantage of the properties mentioned above, Fe-MET electrodes give prominence to electrochemical capacitor (EC) performance by delivering an astounding gravimetric (304 F g-1) and areal (181 mF cm-2) capacitance at 0.5 A g-1 current density with exceptionally high cycling stability. Implementation of Fe-MET as an exclusive (by not using any conductive additives) EC electrode in solid-state energy storage devices outperforms most of the reported MOF-based EC materials and even surpasses certain porous carbon and graphene materials, showcasing superior capabilities and great promise compared to various other alternatives as energy storage materials.

Supercapacitors: An Efficient Way for Energy Storage Application.

To date, batteries are the most widely used energy storage devices, fulfilling the requirements of different industrial and consumer applications. However, the efficient use of renewable energy sources and the emergence of wearable electronics has created the need for new requirements such as high-speed energy delivery, faster charge-discharge speeds, longer lifetimes, and reusability. This leads to the need for supercapacitors, which can be a good complement to batteries. However, one of their drawbacks is their lower energy storage capability, which has triggered worldwide research efforts to increase their energy density. With the introduction of novel nanostructured materials, hierarchical pore structures, hybrid devices combining these materials, and unconventional electrolytes, significant developments have been reported in the literature. This paper reviews the short history of the evolution of supercapacitors and the fundamental aspects of supercapacitors, positioning them among other energy-storage systems. The main electrochemical measurement methods used to characterize their energy storage features are discussed with a focus on their specific characteristics and limitations. High importance is given to the integral components of the supercapacitor cell, particularly to the electrode materials and the different types of electrolytes that determine the performance of the supercapacitor device (e.g., storage capability, power output, cycling stability). Current directions in the development of electrode materials, including carbonaceous forms, transition metal-based compounds, conducting polymers, and novel materials are discussed. The synergy between the electrode material and the current collector is a key factor, as well as the fine-tuning of the electrode material and electrolyte.

Direct carbonization of cellulose toward hydroxyl-rich porous carbons for pseudocapacitive energy storage.

Designing carbon materials with specific oxygen-containing functional groups is very attractive for the precise decoration of carbon electrode materials and the basic understanding of specific charge storage mechanisms, which contributes to the further development of high-performance carbon materials for energy storage and conversion applications. In this contribution, a hydroxyl-rich micropore-dominated porous carbon material was obtained by direct carbonization of cellulose. The content of oxygen atoms in hydroxyl form in the obtained carbon is nearly 6 at.%. With the pyrolysis temperature changed, the macroscopic morphology, the specific surface area, surface functional groups, and graphitization degree of the carbon materials were changed strongly. Besides, the carbon material obtained with a carbonization temperature of 900 °C (C9) showed enhanced specific capacitance in sulfuric acid, sodium hydroxide, and sodium sulfate aqueous electrolytes, which mainly originates from the contribution of pseudocapacitance. The pseudocapacitance mainly depends on the presence of surface hydroxyl functional groups. Besides, the pseudocapacitance value of C9 material in neutral electrolytes (151.34 F g-1) is about twice that in acidic (75.9 F g-1) and alkaline (75.78 F g-1) electrolytes.

MOP-18-Derived CuO Fiber for Hybrid Supercapacitor Electrodes.

This study explores a simple method of fabricating hybrid supercapacitor electrodes, which could potentially broaden the application of this technology. The method involves electrospinning a uniform solution of Matrimid/Metal-Organic Polyhedra 18 (MOP-18) followed by carbonization at a relatively low temperature of 700 °C in air, rather than in an inert atmosphere, to create free-standing, redox-active hybrid supercapacitor electrodes. Additionally, the synthesis procedure requires no stabilization or activation steps, which enhances the cost effectiveness of the synthesized electrode materials. The resulting C/CuO composite was used as the working electrode, with a polyacrylonitrile (PAN)/Poly(methyl methacrylate) (PMMA) carbon nanofiber (CNF) electrode as the counter and 6 M KOH as the electrolyte in a T-cell configuration. The cell performance and redox activity were evaluated using cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), electrochemical impedance spectroscopy (EIS) and cycling stability tests. Additionally, the physical and chemical structures of the electrode materials were assessed using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron spectroscopy (TEM), X-ray diffractometry (PXRD), surface area analysis and other characterization techniques. The electrode material demonstrated a specific capacitance of up to 206 F/g. Supercapacitors utilizing this material display an energy density of 10.3 Wh/kg (active material) at a current density of 1 A/g in electrochemical testing.

Tuning MXene Properties through Cu Intercalation: Coupled Guest/Host Redox and Pseudocapacitance.

MXenes are 2D transition metal carbides, nitrides, and/or carbonitrides that can be intercalated with cations through chemical or electrochemical pathways. While the insertion of alkali and alkaline earth cations into Ti3C2Tx MXenes is well studied, understanding of the intercalation of redox-active transition metal ions into MXenes and its impact on their electronic and electrochemical properties is lacking. In this work, we investigate the intercalation of Cu ions into Ti3C2Tx MXene and its effect on its electronic and electrochemical properties. Using X-ray absorption spectroscopy (XAS) and ab initio molecular dynamics (AIMD), we observe an unusual phenomenon whereby Cu2+ ions undergo partial reduction upon intercalation from the solution into the MXene. Furthermore, using in situ XAS, we reveal changes in the oxidation states of intercalated Cu ions and Ti atoms during charging. We show that the pseudocapacitive response of Cu-MXene originates from the redox of both the Cu intercalant and Ti3C2Tx host. Despite highly reducing potentials, Cu ions inside the MXene show an excellent stability against full reduction upon charging. Our findings demonstrate how electronic coupling between Cu ions and Ti3C2Tx modifies electrochemical and electronic properties of the latter, providing the framework for the rational design and utilization of transition metal intercalants for tuning the properties of MXenes for various electrochemical systems.

Role of Surface Terminations for Charge Storage of Ti3C2Tx MXene Electrodes in Aqueous Acidic Electrolyte.

In this study, we used 2-Dimmensionnal Ti3C2 MXene as model materials to understand how the surface groups affect their electrochemical performance. By adjusting the nature of the surface terminations (Cl-, N/O-, and O-) of Ti3C2 MXene through a molten salt approach, we could change the spacing between MXene layers and the level of water confinement, resulting in significant modifications of the electrochemical performance in acidic electrolyte. Using a combination of techniques including in-operando X-ray diffraction and electrochemical quartz crystal microbalance (EQCM) techniques, we found that the presence of confined water results in a drastic transition from an almost electrochemically inactive behavior for Cl-terminated Ti3C2 to an ideally fast pseudocapacitive signature for N,O-terminated Ti3C2 MXene. This experimental work not only demonstrates the strong connection between surface terminations and confined water but also reveals the importance of confined water on the charge storage mechanism and the reaction kinetics in MXene.

High-performance flexible asymmetric supercapacitor based on hierarchical MnO2/PPy nanocomposites covered MnOOH nanowire arrays cathode and 3D network-like Fe2O3/PPy hybrid nanosheets anode.

The configuration of asymmetric supercapacitors (ASCs) has proven to be an effective approach to increase the energy storage properties due to the expanded working voltage resulting from the well-separated potential windows of the cathode and anode. However, carbonaceous anode materials generally suffer from relatively low capacitance, which restricts the enhancement of the energy storage performance of the full device in a traditional asymmetrical design. Herein, a rational design of all-pseudocapacitive ASCs (APASCs) using pseudocapacitive materials with a novel hierarchical nanostructure on both electrodes was developed to optimize the electrochemical properties for high-performance ASC devices. The assembled APASC employed the MnO2/PPy nanocomposites covered MnOOH nanowire arrays with core-shell hierarchical architecture as the cathode and Fe2O3/PPy hybrid nanosheets with 3D porous network-like structure as the anode. Owing to the coordinated pseudocapacitive properties and unique hierarchical nanostructures, this assembled APASC exhibited an exceptional volumetric capacitance of 4.92F cm-3 in a stable voltage window of 2 V, a maximum volumetric energy density of 2.66 mWh cm-3 at 19.72 mW cm-3, and excellent cyclic stability over 10,000 cycles (90.6 % capacitance retention), as well as remarkable flexibility and mechanical stability, providing insights for the design of flexible energy storage systems with enhanced performance.

Electrochemical Capacitance Traces with Interlayer Spacing in Two-dimensional Conductive Metal-Organic Frameworks.

Electrically conductive metal-organic frameworks (MOFs) are promising candidates for electrochemical capacitors (EC) for fast energy storage due to their high specific surface areas and potential for redox activity. To maximize energy density, traditional inorganic pseudocapacitors have utilized faradaic processes in addition to double-layer capacitance. Although conductive MOFs are usually comprised of redox active ligands which allow faradaic reactions upon electrochemical polarization, systematic studies providing deeper understanding of the charge storage processes and structure-function relationships have been scarce. Here, we investigate the charge storage mechanisms of a series of triazatruxene-based 2D layered conductive MOFs with variable alkyl functional groups, Ni3(HIR3-TAT)2 (TAT=triazatruxene; R=H, Et, n-Bu, n-Pent). Functionalization of the triazatruxene core allows for systematic variation of structural parameters while maintaining in-plane conjugation between ligands and metals. Specifically, R groups modulate interlayer spacing, which in turn shifts the charge storage mechanism from double-layer capacitance towards pseudocapacitance, leading to an increase in molar specific capacitance from Ni3(HIH3-TAT)2 to Ni3(HIBu3-TAT)2. Partial exfoliation of Ni3(HIBu3-TAT)2 renders redox active ligand moieties more accessible, and thus increases the dominance of faradaic processes. Our strategy of controlling charge storage mechanism through tuning the accessibility of redox-active sites may motivate further design and engineering of electrode materials for EC.

Regulating Crystal Orientation in VO2 for Aqueous Zinc Batteries with Enhanced Pseudocapacitance.

Although aqueous zinc batteries have attracted extensive interest, they are limited by relatively low rate capabilities and poor cyclic stability of cathodes. The crystal orientation of the cathode is one important factor influencing electrochemical properties. However, it has rarely been investigated. Herein, VO2 cathodes with different crystal orientations are developed via tuning the number of hydroxyl groups in polyol, such as using glycerol, erythritol, xylitol, or mannitol. The polyols serve as a reductant as well as a structure-directing agent through a hydrothermal reaction. Xylitol-derived VO2 shows a (110)-orientated crystalline structure and ultrathin nanosheet morphology. Such features greatly enhance the pseudocapacitance to 76.1% at a scan rate of 1.0 mV s-1, which is significantly larger than that (61.6%) of the (001)-oriented VO2 derived from glycerol. The corresponding aqueous zinc batteries exhibit a high energy storage performance with a reversible specific capacity of 317 mAh g-1 at 0.5 A g-1, rate ability of 220 mAh g-1 at 10 A g-1, and capacity retention of 81.0% at 10 A g-1 over 2000 cycles. This work demonstrates a facile method for tailoring VO2 crystal orientations, offers an understanding of the Zn2+ storage mechanism upon different VO2 facets, and provides a novel method to develop cathode materials toward advanced aqueous zinc batteries.

Effect of annealing temperature on structural and electrochemical behaviour on MgFe2O4as electrode material in neutral aqueous electrolyte for supercapacitors.

Binary metal oxides possess unique structures and multiple oxidation states, making them highly valuable in electrochemical analysis. This study aims to determine the effect of annealing temperature on the electrochemical properties of magnesium ferrite when used as an electrode material in a neutral aqueous electrolyte. We utilized the sol-gel technique to synthesize the material and annealed it at various temperatures. Our analysis of the material using different characterization techniques reveals significant changes in its structural and electrochemical properties. We found that the material exhibited a range of phases, and higher annealing temperatures led to improved electrochemical properties. The electrochemical measurements showed reversible and redox pseudo-capacitance behavior, with the material annealed at 500 °C exhibiting the highest specific capacitance of 117 F g-1at a current density of 0.5 A g-1. Capacitive and diffusion-controlled processes govern the total charge storage mechanism, and their contribution changes significantly as the annealing temperature varies. The capacitance retention of 500 °C annealed sample was 58% and it remained stable. This work establishes a correlation between annealing temperature on structural, morphological, and electrochemical behavior, thereby opening up avenues for tailoring them effectively. These findings can be useful in the development of future electrode materials for electrochemical applications.

Ultrafast and Durable Sodium-Ion Storage of Pseudocapacitive VN@C Hybrid Nanorods from Metal-Organic Framework.

Vanadium nitride (VN) is a promising electrode material for sodium-ion storage due to its multivalent states and high electrical conductivity. However, its electrochemical performance has not been fully explored and the storage mechanism remains to be clarified up to date. Here, the possibility of VN/carbon hybrid nanorods synthesized from a metal-organic framework for ultrafast and durable sodium-ion storage is demonstrated. The VN/carbon electrode delivers a high specific capacity (352 mA h g-1), fast-charging capability (within 47.5 s), and ultralong cycling stability (10 000 cycles) for sodium-ion storage. In situ XRD characterization and density functional theory (DFT) calculations reveal that surface-redox reactions at vanadium sites are the dominant sodium-ion storage mechanism. An energy-power balanced hybrid capacitor device is verified by assembling the VN/carbon anode and active carbon cathode, and it shows a maximum energy density of 103 Wh kg-1 at a power density of 113 W kg-1.

Supramolecular Engineering of Ti3C2Tx MXene -Perylene Diimide Hybrid Electrodes for the Pseudocapacitive Electrochemical Storage of Calcium Ions.

The rare combination of metallic conductivity and surface redox activity enables 2D MXenes as versatile charge storage hosts for the design of high-rate electrochemical energy storage devices. However, high charge density metal ions including but not limited to Ca+2 and Mg+2 pose challenges such as sluggish solid-state diffusion and also inhibiting the charge transfer across electrode-electrolyte interfaces. In this work, free-standing hybrid electrode architectures based on 2D titanium carbide-cationic perylene diimide (Ti3C2Tx@cPDI) via supramolecular self-assembly are developed. Secondary bonding interactions such as dipole-dipole and hydrogen bonding between Ti3C2Tx and cPDI are investigated by zeta potential and Fourier-transformed infrared (FTIR) spectroscopy . Ti3C2Tx@cPDI free-standing electrodes show typical volumetric capacitance up to 260 F cm-3 in Mg2+ and Ca2+ aqueous electrolytes at charging times scales from 3 minutes to a few seconds. Three-dimensional (3D) Bode maps are constructed to understand the charge storage dynamics of Ti3C2Tx@cPDI hybrid electrode in an aqueous Ca-ion electrolyte. ,Pseudocapacitance is solely contributed by the nanoscale distribution of redox-active cPDI supramolecular polymers across 2D Ti3C2Tx. This study opens avenues for the design of a wide variety of MXene@redox active organic charge hosts for high-rate pseudocapacitive energy storage devices.

Processing mechanism synergizing surface and intercalation pseudocapacitance engineering fast-charging Li-based anode materials.

Pseudocapacitive material can achieve rapid charge and discharge response. In this study, a vanadium-based conductive network hydrate (Na0.13Mg0.02)V2O5·0.98H2O (NMVO) was designed. The Na+ and Mg2+ in NMVO are sandwiched between two layers of vacancy-ordered prisms and monoclinic nanonetwork V3O7 (VO2:V2O5 = 1:1) to form a conductive network with a layer spacing of up to 11.67 Å, this structure facilitates rapid interlayer diffusion of cations and enhanced conductivity. Reduction-NMVO (r-NMVO) with hierarchical heterostructures was prepared via an in-situ electrochemical process to generate interlayer vanadium-based active sites (LiV3O8, LiV2O5, Na3V3O8, MgVO3) with multi-electron reaction, which enhanced the generation of surface redox pseudocapacitance. The interlayer heterostructure is integrated with the core of the precursor V3O7 to form an active site-rich conductive network with strong pulse impact resistance, which promotes the generation of intercalated pseudocapacitance and increases the cycle stability of the electrode. This intercalation-surface redox pseudocapacitive mechanism was confirmed by first-principles, in-situ, and ex-situ characterization analysis. The r-NMVO|Li battery still maintains a capacity of 95.5 % after 65,500 cycles at a current density of 50 A g-1. These results contribute directly to the realization of stable, fast charge and discharge material design.

Proton is Essential or Not: A Fresh Look on Pseudocapacitive Energy Storage of PANI Composites.

Protonation has been considered essential for the pseudocapacitive energy storage of polyaniline (PANI) for years, as proton doping in PANI chains not only activates electron transport pathways, but also promotes the proceeding of redox reactions. Rarely has the ability for PANI of storing energy without protonation been investigated, and it remains uncertain whether PANI has pseudocapacitive charge storage properties in an alkaline electrolyte. Here, this work first demonstrates the pseudocapacitive energy storage for PANI without protonation using a PANI/graphene composite as a model material in an alkaline electrolyte. Using in situ Raman spectroscopy coupled with electrochemical quartz crystal microbalance (EQCM) measurements, this work determines the formation of -N= group over potential on a PANI chain and demonstrates the direct contribution of OH- in the nonprotonation type of oxidation reactions. This work finds that the PANI/graphene composite in an alkaline electrolyte has excellent cycling stability with a wider operation voltage of 1 V as well as a slightly higher specific capacitance than that in an acidic electrolyte. The findings provide a new perspective on pseudocapacitive energy storage of PANI-based composites, which will influence the selection of electrolytes for PANI materials and expand their application in energy storage fields.