Electrochemical Energy Storage Performance Research Articles

Synergistic Corrosion Engineering on Metallic Manganese Toward High‐Performance Electrochemical Energy Storage

AbstractMnO/rGO with enhanced electrochemical kinetic properties is widely investigated as electrode for high‐performance electrochemical energy storage (EES) devices. However, the synthesis of MnO/rGO via traditional methods suffers from low atomic utilization and complex techniques that are undesirable for practical implementation. Different from existing fabrication strategies, here using metallic manganese as Mn source, a novel, eco‐friendly, and corrosion engineering‐based approach to address the above issues is demonstrated. It is thermodynamically feasible as supported by the E‐pH analysis and for the first time, a significant synergetic effect is observed between NH4+ and GO in strengthening the metallic Mn corrosion reaction. Particularly, in the “ammonia circulation” process, the NH3 molecule, derived from NH4+, acts as a “carrier” for Mn2+ to facilitate its transfer by forming [Mn(NH3)2]2+, which effectively prevents “in situ corrosion”. The phase and structure evolution during the reaction are clarified, and the synergistic corrosion mechanism is also proposed. Benefiting from the efficient lithium‐ion evolution kinetics, Mn─O─C bond formed between MnO and rGO and outstanding structural integrity, the resultant MnO/rGO demonstrates exceptional EES performances in both lithium‐ion batteries and lithium‐ion capacitors. This finding will offer potential for mild, cost‐effective, and environmentally friendly fabrication of other graphene‐based metal oxide electrodes using corrosion engineering.

Enhanced electrochemical energy storage performance by mediating BaTiO3 nanoparticles into the multilayers of Ti3C2Tx MXene

MXenes belong to the family of two-dimensional (2D) transition metal carbides, have been identified as advanced energy materials with exceptional performance. In this paper, we employed a strategy to intercalate BaTiO3 (BTO) nanoparticles into the two-dimensional (2D) Ti3C2Tx MXene sheets and use as electrode materials for electrochemical performances. BTO intercalated MXenes prove more active areas for improved electrochemical performance. As a result, the BTO intercalated Ti3C2Tx MXene electrode exhibits a high specific capacitance of 254.28F/g at 1 A/g and a retention ratio 74% after 10,000 cycles. The electrochemical stability study confirms that restacking issues were resolved. Thus, the intercalation of BTO enhanced the reaction kinetics of the MXenes and facilitate the charge storage valuable mechanism for next-generation smart energy storage devices.

Sonochemically synthesized novel CNTs-PANI/CoNi(PO4)2 nanocomposites with enhanced electrochemical energy storage performance for asymmetric supercapacitor applications

Carbon nanotubes (CNTs) were polymerized with polyaniline (PANI) via an in-situ polymerization approach. These functionalized CNTs (PANI-CNTs) were added in various concentrations to the sono-chemically synthesized Co-Ni binary transition metals phosphate (CoNi(PO4)2) to ultimately have their nanocomposites. Electron microscopy (SEM & HRTEM) was employed to reveal the morphology and microscopic features. The structural evaluation of metal phosphate and PANI/CNTs was done by X-ray diffractometer analysis, whereas chemical grafting of cobalt nickel phosphate (CoNi(PO4)2) was done by Fourier transformed infrared spectroscopy and Raman spectroscopy. The hierarchical structured CoNi(PO4)2 with 40 mg PANI/CNTs mass (CNP40) presented enhanced specific capacity of 1268 Cg−1 (2136 F g−1 at 1.5 F g−1) with excellent diffusive behavior (b = 0.5). A resulted hybrid supercapacitor device consisting of CNP40 as +ve electrode and activated carbon AC) as −ve electrode, presented excellent energy density of ∼87 Whkg−1 with good power density of 680 W kg−1 maintained to 32.9 W kg−1 (@ 20,400 W kg−1) with 37% rate performance, and excellent cyclic performance (∼100%) after 5000 charge-discharge cycles. Furthermore, capacitive-diffusive analysis revealed that the device showed 55% diffusive and 45% capacitive behaviour. This improved electrochemical performance might be attributed mainly to the uniform and hierarchical chemical grafted morphology of the novel combination of binary phosphates and PANI functionalized CNTs in the nanocomposite obtained via a rather different sonochemical approach.

Morphology-controlled synthesis of a NiCo-carbonate layered double hydroxide as an electrode material for solid-state asymmetric supercapacitors

NiCo-carbonate layered double hydroxides of diverse morphologies, such as nanorod, microcube, microplate and urchin-like, are synthesized by a single-step synthesis and their electrochemical energy storage performance is evaluated.

Enhanced hydrogen evolution and symmetric supercapacitor performance of a Ru-doped multiphase WS2 electrode

The metallic and semiconductive phase (1T/2H) coupling enhanced electrochemical energy generation and storage performance of the Ru-doped WS2 multifunctional electrode is reported here.

Element screening of metal sites in Fe-based Prussian blue framework materials for ammonium ion battery applications: a first-principles study.

Prussian blue framework materials are expected to be the next generation of electrode materials for commercial batteries because their three-dimensional framework structures facilitate the rapid transport and storage of ions and a variety of redox processes. This work compared the calculations of the model before and after the dispersion correction, and the model considering the effect of van der Waals force was more stable. In addition, the distances between H, C and N atoms were within the range of van der Waals force. Thus it was confirmed that NH4+ was adsorbed on the Ax site in the Prussian blue framework material (AxMa[Mb(CN)6]) by van der Waals interaction, and the charge transfer was mainly achieved by the interaction between the H atom in NH4+ and the N atom in the Prussian blue framework. On this basis, the properties of NH4+ batteries were theoretically screened for the Fe-based Prussian blue analogues (PBAs) with different Ma elements (Ma = Co, Cu, Fe, Mg, Mn, Ni, V or Zn). Considering the regulating effect of different metal elements on the electronic structures of PBAs, MgFe and ZnFe PBAs as the electrode materials of NH4+ batteries are expected to show excellent electrochemical energy storage performance in organic electrolytes.

Electrochemical energy storage performance of one-step laser written Cu-C composites

One-step laser written copper-carbon (Cu-C) composites are ideal for assembling supercapacitors, but their structuring-performance correlation remains unclear. In this study, the microstructure of written composites has been controlled by varying the laser power. Their electrochemical energy storage performance has been investigated and compared to reveal the contribution of each component. The porous carbon-rich (C-rich) structure, introduced by laser carbonization of the substrate, can provide abundant active sites for the Faraday reaction of the copper-rich (Cu-rich) structure. The continuous sintered Cu-rich structure, obtained by laser reduction of ionic precursor and in-situ joining, can ensure fast transfer of electrons in the composites. Owing to their synergistic effect, our optimal composite exhibits an excellent specific capacity of 107.2 C/cm2 at 1 mA/cm2. This study provides a theoretical reference for the development of high-performance supercapacitors.

Phosphorus-Doped Nickel Oxide Micro-Supercapacitor: Unleashing the Power of Energy Storage for Miniaturized Electronic Devices.

For an uninterrupted self-powered network, the requirement of miniaturized energy storage device is of utmost importance. This study explores the potential utilization of phosphorus-doped nickel oxide (P-NiO) to design highly efficient durable micro-supercapacitors. The introduction of P as a dopant serves to enhance the electrical conductivity of bare NiO, leading to 11-fold augmentation in volumetric capacitance to 841.92 Fcm-3 followed by significant enhancement of energy and power density from 6.71 to 42.096 mWhcm-3 and 0.47 to 1.046 Wcm-3, respectively. Theoretical calculations used to determine the adsorption energy of OH- ions, revealing higher in case of bare NiO (1.52eV) as compared to phosphorus-doped NiO (0.64eV) leading to high electrochemical energy storage performance. The as-designed micro-supercapacitor (MSC) device demonstrates a facile integration with the photovoltaic system for renewable energy storage and smooth transfer to external loads for enlightening the blue LED for ≈1min. The choice of P-NiO/Ni not only contributes to cost reduction but also ensures minimal lattice mismatch at the interface facilitating high durability up to 15 K cycles along with capacitive retention of ≈100% and coulombic efficiency of 93%. Thus, the heterostructure unveils the possibilities of exploring miniaturized energy storage devices for portable electronics.

Facile synthesis of free-binder (NiCo)x(CuZn)1-xMoO4 (x = 0, 0.25, 0.5, 0.75, and 1)/nickel foam electrodes for supercapacitor application

In this work, free-binder (NiCo)x(CuZn)1-xMoO4 (x = 0, 0.25, 0.5, 0.75, and 1)/nickel foam electrodes were prepared by cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal synthesis method. The composition modulated the morphology of material deposited on the nickel foam due to the different interactions between various cations and MoO42− species. With the increase of the Ni and Co contents, the morphology of molybdates transformed from agglomerated spherical particles to the flower-like hierarchal 2D flakes. Therefore, the application of multicomponent can be improved the electrochemical performance via tuning the morphology and physicochemical properties. The (NiCo)0.5(CuZn)0.5MoO4/nickel foam electrode with flower-like morphology showed the highest specific capacitance of 1176 F g−1 at a current density of 1 A g−1 and significant rate capability of 83 % (980 F g−1 up to 5 A g−1). The hierarchal flower-like (NiCo)0.5(CuZn)0.5MoO4//activated carbon asymmetric capacitor offered the rather high performance for electrochemical energy storage including energy density of 41.5 Wh kg−1 at power density of 1450 W kg−1.

Hollow Polyaniline Helical Nanobelts toward Efficient Electrochemical Energy Storage and Adsorption Performance

Hollow Polyaniline Helical Nanobelts toward Efficient Electrochemical Energy Storage and Adsorption Performance

Redox-active 9,10-phenanthrenequinone non-covalently modify reduced graphene oxide for high-performance asymmetric supercapacitor and zinc-ion hybrid capacitors

Redox-active organic molecules show great potential in novel renewable energy storage devices by modifying carbon-based materials in covalent or non-covalent forms due to their light-weight, rich structural diversity, good designability and abundance. Herein, we synthesized redox-active 9,10-phenanthrenequinone (PQ) molecules non-covalently modified reduced graphene oxide (RGO) nanocomposites by an improved simple one-step solvothermal method and explored their application as advanced electrode in aqueous energy storage devices. Benefiting from the rich redox-active sites brought by the anchored PQ molecules and the formation of the hierarchical porous network nanostructures with the RGO substrates that facilitates the charge transport and ion diffusion kinetics, the synthesized RGO/PQs nanocomposites exhibit significantly enhanced electrochemical energy storage performance. The optimal RGO/PQ-1.5 electrode has a high specific capacitance of 383.3 F g−1 at 0.5 A g−1 and good rate capability. And the asymmetric supercapacitor (ASC) assembled with the N-RGO negative electrode exhibits significantly better energy density than pure carbon electrode ASCs. More surprisingly, the assembled RGO/PQ-1.5//Zn zinc-ion hybrid capacitor exhibits an attractive specific capacity of 139.4 mAh g−1, a high energy density of 134.6 Wh kg−1, and an ultra-long cycling stability with 95.3 % capacity retention after 14,000 cycles, demonstrating excellent zinc-ion energy storage performance.

Surface‐amorphized nickel sulfide with boosted electrochemical performance for aqueous energy storage

AbstractThe ingenious structural design of electrode materials has a great influence on boosting the integrated conductivity and improving the electrochemical behavior of energy storage equipment. In this work, a surface‐amorphized sandwich‐type Ni3S2 nanosheet is synthesized by an easy hydrothermal and solution treatment technique. Because of the in‐built defect‐rich feature of the amorphous Ni3S2 layer, the constructed crystalline/amorphous heterointerface as well as dual nanopore structure of Ni3S2 nanosheet, the electron/ion transport and interfacial charge transfer is boosted, which contribute to high ionic conductivity and low resistance of the SA‐Ni3S2 electrode. The SA‐Ni3S2 electrode shows high specific capacitance (1767.6 F g−1 at 0.5 A g−1); the SA‐Ni3S2//AC device delivers high specific capacitance (131.2 F g−1 at 0.2 A g−1) and outstanding cycle stability (75% capacitance retention after 10000 cycles). In Ni‐Zn battery measurement, the SA‐Ni3S2//Zn exhibits satisfying specific capacity (211.2 mAh g−1 at 0.5 A g−1) and cycle durability (68% capacity decay after 2000 cycles). The results imply that the rational design of surface‐amorphized heterostructure is helpful for fabrication of electrode materials with high electrochemical performance in energy storage applications.

Defect engineering on BiFeO3 through Na and V codoping for aqueous Na-ion capacitors

Sodium with low cost and high abundance is considered as a substitute element of lithium for batteries and supercapacitors, which need the appropriate host materials to accommodate the relatively large Na+ ions. Compared to Li+ storage, Na+ storage makes higher demands on the structural optimization of perovskite bismuth ferrite (BiFeO3). We propose a novel strategy of defect engineering on BiFeO3 through Na and V codoping for high-efficiency Na+ storage, to reveal the roles of oxygen vacancies and V ions played in the enhanced electrochemical energy storage performances of Na-ion capacitors. The formation of the oxygen vacancies in the Na and V codoped BiFeO3 (denoted as NV-BFO), is promoted by Na doping and suppressed by V doping, which can be demonstrated by XPS and EPR spectra. By the first-principles calculations, the oxygen vacancies and V ions in NV-BFO are confirmed to substantially lower the Na+ migration energy barriers through the space and electric field effects, to effectively promote the Na+ transport in the crystals. Electrochemical kinetic analysis of the NV-BFO//NV-BFO capacitors indicates the dominant capacitive-controlled capacity, which depends on fast Na+ deintercalation-intercalation process in the NV-BFO electrode. The NV-BFO//NV-BFO capacitors open up a new avenue for developing high-performance Na-ion capacitors.

ZIF-derived hollow cattail-shaped composites with hierarchical channels towards enhanced electrochemical properties for supercapacitors

Despite the achievement in generating various hollow architectures, designing hollow composites with hierarchical channels remains challenging to achieve excellent electrochemical energy storage performance. To address this issue, we developed an in situ self-assembly strategy to prepare hollow composites using zeolitic-imidazolate frameworks and carbon nanotubes (ZIF@CNT). These ZIF@CNT architectures with different appearances are prepared by adjusting the stirring rate during the reaction. Subsequently, the sulfurization strategy is applied to convert ZIF-67 to cobalt sulfide (CoS), resulting in the hollow CoS@CNT hybrids. These hierarchical channels include the hollow CoS cavities and CNT channels. The unique hollow composites with different dimensions played a synergistic effect between subunits, thus giving excellent electrochemical properties. The impact of particle cavity channel size on electrochemical properties was evaluated systematically. As expected, CoS@CNT with hollow cattail-shape structures (HCCoS@CNT) resulted in the optimal specific capacitance (1250 F/g) and cyclic stability (90.4 % for over 10,000 times of cycling at 10 A/g). The designed hybrid supercapacitor, HCCoS@CNT//active carbon (AC), delivered an exceptional energy density of 40 Wh kg−1 at 800 W kg−1 of the power density. Together, these findings provide a reference for preparing complex hollow structures as high-performance electrodes, clarifying the optimization of composites for improved electrochemical properties.

Electrochemical synthesis of some thiosemicarbazide derivatives doped polypyrrole electrodes and supercapacitor applications

Thiosemicarbazide derivatives (TSC, N-Phenyl TSC, N-Cyclohexyl TSC) doped polypyrrole (PPy) based electrodes were synthesized in one step electropolymerization method. It was determined that thiosemicarbazide derivatives had an effect on the morphological and chemical structure of PPy. Among the thiosemicarbazide derivatives, it was determined that the additive of PPy that had the highest and most curative effect on the electrochemical energy storage performance was determined to be N-Cyclohexyl TSC, and its effects on the electrochemical performance at different concentrations were investigated. The PPy/N-Cyclohexyl TSC (2.5 mM) electrode exhibited a capacitance of 300.5 F/g at a potential operating range of 1.1 V, in 0.5 M H2SO4 electrolyte, and the current density of 0.5 A/g. The symmetrical supercapacitor device obtained using PPy/N-Cyclohexyl TSC (2.5 mM) electrode showed capacitance retention rate of 90.4% and 81.5% in 0.5 M H2SO4 and 1.0 M Na2SO4 electrolytes and at the end of the 5000 cycles life cycle test, respectively. In addition, the PPy/N-Cyclohexyl TSC (2.5 mM)/ PPy/N-Cyclohexyl TSC (2.5 mM) symmetrical supercapacitor device exhibits a specific capacitance of 175 F/g at a current density of 0.4 A/g in 0.5 M H2SO4, while 137.3 F/g in 1.0 M Na2SO4 electrolyte. The energy and power density values obtained at 0.5 M H2SO4 and 1.0 M Na2SO4 for the supercapacitor device were 8.7 Wh/kg, 343.4 W/kg and 19.1 Wh/kg, 883.5 W/kg, respectively.

Molecular engineering assembly of mesoporous carbon onto Ti3C2Tx MXene for enhanced lithium‐ion storage

AbstractThe rational construction of Ti3C2Tx MXene‐based composites has been deemed as a popular way to improve their electrochemical energy storage performances owing to the unique two‐dimensional (2D) structure, excellent conductivity, and good flexibility. However, it remains a major challenge to assemble mesoporous carbon onto Ti3C2Tx with fewer oxygen‐containing groups by using surfactants with short hydrophilic segments. In the work, we propose a molecular engineering assembly strategy for the growth of N,P co‐doped mesoporous carbon onto Ti3C2Tx nanosheets (NPMC/Ti3C2Tx) under the assistance of phytic acid by using melamine‐formaldehyde resin and pluronic P123 (PEO20PPO70PEO20) as the carbon/nitrogen source and soft template, respectively. The detailed investigations reveal that phytic acid with abundant hydroxyl groups can effectively enhance the hydrogen bond interactions among P123, carbon precursor, and Ti3C2Tx nanosheets, thus ensuring the efficient assembly of mesoporous carbon onto Ti3C2Tx. The obtained NPMC/Ti3C2Tx composite demonstrates a set of merits, including cylindrical mesopore, N,P co‐doping, and a good combination of mesoporous carbon and Ti3C2Tx nanosheets. As a result, it exhibits an improved lithium‐ion storage performance, delivering a high reversible capacity of 556.3 mA h g−1 after 100 cycles at 0.1 A g−1. The present work provides a feasible molecular engineering assembly route for the rational design of high‐performance Ti3C2Tx MXene‐based electrodes.

Boosting electrochemical and photocatalytic performance of Cadmium Sulfide/Zinc Telluride nanocomposites via Nickel doping

Nanocomposites offer boosted performance for electrochemical energy storage and photocatalytic applications in response to the rising need for effective and sustainable energy storage solutions. In this study, multifunctional Nickel-doped Cadmium Sulfide/Zinc Telluride (Ni-CdS/ZnTe) nanocomposites were fabricated using a sonochemical approach to improve energy storage and enhance photocatalytic activity. The optimized sample (5 % Ni-CdS/ZnTe nanocomposites) displayed boosted photocatalytic activity and degraded MB, MO, and RhB dyes up to 98.74 %, 99.71 %, and 95.03 %, respectively in 45 min of exposure to visible light. For the first time, the electrochemical properties of Ni-CdS/ZnTe nanocomposites were also investigated. The 5 % Ni-CdS/ZnTe nanocomposite-based electrode exhibited an impressive specific capacitance of 517.6F/g, a remarkable energy density of 17.97 W h/Kg, and a boosted power density of 250 W/kg at a current density of 1 A/g. These findings offer new possibilities for the utilization of Ni-CdS/ZnTe nanocomposites in environment and energy storage applications.

X-ray Spectroscopy Study of Defect Contribution to Lithium Adsorption on Porous Carbon.

Lithium adsorption on high-surface-area porous carbon (PC) nanomaterials provides superior electrochemical energy storage performance dominated by capacitive behavior. In this study, we demonstrate the influence of structural defects in the graphene lattice on the bonding character of adsorbed lithium. Thermally evaporated lithium was deposited in vacuum on the surface of as-grown graphene-like PC and PC annealed at 400 °C. Changes in the electronic states of carbon were studied experimentally using surface-sensitive X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. NEXAFS data in combination with density functional theory calculations revealed the dative interactions between lithium sp2 hybridized states and carbon π*-type orbitals. Corrugated defective layers of graphene provide lithium with new bonding configurations, shorter distances, and stronger orbital overlapping, resulting in significant charge transfer between carbon and lithium. PC annealing heals defects, and as a result, the amount of lithium on the surface decreases. This conclusion was supported by electrochemical studies of as-grown and annealed PC in lithium-ion batteries. The former nanomaterial showed higher capacity values at all applied current densities. The results demonstrate that the lithium storage in carbon-based electrodes can be improved by introducing defects into the graphene layers.

High performance polythiophene derivative with good electrochromic and energy storage properties electrochemical synthesized in boron trifluoride diethyl etherate

In this study, novel poly(3,4-dibromothiophene) (PDBrTh) is firstly prepared through electrochemical polymerization method using boron trifluoride diethyl etherate (BF3·Et2O) as polymeric solvent. In BF3·Et2O, the electrochemical oxidation potential of 3,4-dibromothiophene is significantly reduced compared with in Acetonitrile/Tetrabutylammonium tetrafluoroborate (ACN/TBATFB) system, which provides conditions for high quality polymer preparation. The prepared PDBrTh in BF3·Et2O shows good electrochemical activity and thermal stability. The electrochromic and supercapacitive performance of the prepared PDBrTh are also studied. The color of the prepared PDBrTh can be reversibly changed between red and blue with fast response time and high optical contrast. Galvanostatic charge-discharge test shows that the prepared PDBrTh also has good electrochemical energy storage performance. The specific capacitance value of the PDBrTh can reach to 229.6 F g−1 under the current density of 1 A g−1, showing good energy storage capacity. An all-polythiophenes electrochromic supercapacitor device (ESD) is constructed by prepared PDBrTh and poly(3,4-ethylenedioxythiophene), the color of the device can change between red and dark blue. The ESD also shows good energy storage property and robust charge-discharge stability. Moreover, the ESD shows obvious color changes and corresponding light transmittance changes during the charging and discharging process, realizing intelligent visual monitoring of the energy storage state. This study shows that the prepared PDBrTh has good practical application potential in the field of intelligent wearable energy storage.

Inorganic perovskite photo-assisted supercapacitor for single device energy harvesting and storage applications

Halide-perovskite having excellent electronic, ionic, optoelectronic and optoionic properties have been found suitable for both energy harvesting and energy storage devices. Herein, we exploit these properties to fabricate a photo-assisted supercapacitor serving the dual functions of energy harvesting and electrochemical energy storage in a single device. The device utilized stable inorganic Cu3Bi2I9 perovskite material in fabricating a Cu-perovskite photoactive electrode. A novel HPvA gel electrolyte was synthesized and sandwiched between two Cu-perovskite photoactive electrodes, to obtain a Cu-perovskite photo-assisted supercapacitor. The HPvA gel electrolyte was characterized by fourier-transfrom infrared spectroscopy (FTIR), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). The Cu-perovskite photoactive electrode was characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). We characterized the electrochemical and photo-electrochemical energy storage performance of the Cu-perovskite photo-assisted supercapacitor by cyclic voltammetry (CV) and EIS. The device recorded 127 % energy density augmentation, at a scan rate of 0.01 V/s. The Cu-perovskite photo-assisted supercapacitor retained 93.8 % of its initial capacitance, after 10,000 charge-discharge cycles.