The present invention relates to a self-supported integrated structure of electrode consisting of heteroatoms, and more particularly the utilization of hetero-atomic self-supported metal nitrides for high energy hybrid supercapacitor (HSC) cells.
Background description includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.
There is no doubt that the global energy demand is increasing rapidly owing to the economic growth and increase in human population along with their reliance on energy-related gadgets. The past few decades have witnessed a rapid depletion in fossil fuels, making energy storage devices one of the hot topics in near future. In search of clean and highly efficient energy storage systems, hybrid supercapacitors (HSCs) have been found to be one of the best devices as a result of their ultrahigh power densities along with their stable cycling performance, cost-effectiveness, high efficiency and for being environment friendly. However, the surface controlled electrochemical reactions of supercapacitors restrict the charge transfer process on or near the surface leading to a relatively inferior energy storing capacity than the traditionally used Li-ion batteries (LIBs), which hamper their leading role for practical devices. The hybrid design of supercapacitors assembled with a redox active positive electrode and carbon composed negative electrode can be able to tackle the low energy density limit exclusive of surrendering power density and cycle life. Thus far it has been challenging to find an appropriate electrode material to boost the energy storage capacity of present supercapacitors, and bring the same close to that of LIBs.
Among transition metal-based electrodes, transition metal nitrides (TMNs) have also been employed as a promising class of electrode materials for LIBs, electro catalysis and supercapacitors in recent years. Particularly, TMNs possess several merits of active supercapacitors electrode including their almost metal-like electrical conductivity, novel electronic structure, excellent electrochemical activity, high specific capacity and high resistance to the corrosion. Notably, due to the presence of interstitial nitrogen in their electronic structure, TMNs facilitate quick electron transfer. In particular, Ni3N, Co2N, VN, MoN etc. are explored to be superior electrode materials for supercapacitors. Recently, Cobalt nitride (Co4N) grips huge potential as a novel material for supercapacitors because of the incorporation of nitrogen (N) atoms into the interstitial sites of cobalt unit cells (it offers high electrical conductivity, high intrinsic activity, stable performance).
Nevertheless, practical applications of Co4N-based electrodes are imperfect due to their metastable properties—and to overcome this instability, carbon-based materials are generally used as a matrix to immobilize electrode as protective shells. Recently, N-doped carbon matrix has taken more interest owing to their excellent features including simple preparation, high electronic conductivity and being environment friendly. Interestingly, the carbon atoms from the carbon matrix are replaced with the doped N atoms and the charge transfer takes place between adjacent carbon atoms and doped N atoms, which enhances the conductivity and create more active sites for the electrochemical activity of the electrode. For example, Zhu et al. developed incorporated electrode with Co—TiN encapsulated in N-doped carbon which delivered capacitance of 189 mF cm−2 at a current density of 0.5 mA cm−2. The hetero-structured electrode with Ni-doped Co—Co2N nanosheets arrays were found to deliver maximum specific capacity of 361.93 C g−1 at 2 mA cm−2. Thus, the development towards the fabrication of an extremely pleasing yet self-supported metal nitrides coordinated with N-doped carbon with excellent energy storage capability is highly required however challenging too.
Therefore, there exists a need for self-supported metal nitrides coordinated with N-doped carbon which overcomes the drawbacks faced by traditionally implemented nanosheets or arrays.
Therefore it is an objective of the present invention to propose the utilization of hetero-atomic self-supported metal nitrides for high energy hybrid supercapacitor (HSC) cells, which overcomes the drawbacks faced by traditionally implemented nanosheets or arrays.
In an aspect of the invention, a process of producing a hybrid super-capacitor (HSC) electrode is proposed, the process comprising the steps of performing nitridation-induced in situ coupling of Ni—Co4N nanoparticles in an N-doped carbon matrix, wherein the resultant hybrid super-capacitor (HSC) electrode is a Ni—Co4N@NC electrode.
In an embodiment of the present invention, the resultant hybrid super-capacitor (HSC) electrode is a self-supported metal nitride coordinated with N-doped carbon.
In another embodiment of the present invention, the nitridation-induced in situ coupling is performed via a facile pyrolysis of layered Ni—Co hydroxide decorated on polyaniline (PANI) nanotubes on the basis of a carbon cloth (CC).
In another embodiment of the present invention, nitrogenous gases released from the facile pyrolysis of polyaniline (PANI) nanotubes are used for the in-situ conversion of NiCo@PANI to Ni—Co4N@NC.
In another embodiment of the present invention, the produced hybrid super-capacitor (HSC) electrode is constructed with Ni—Co4N@NC and activated carbon (AC) as cathode and anode of the produced hybrid super-capacitor (HSC) electrode.
In another embodiment of the present invention, the cathode and anode demonstrate a specific energy of 57.2 Wh kg−1 at a specific power of 843.8 W kg−1 and capacity retention of 89.7% after 15,000 cycles.
In another embodiment of the present invention, synthesis of polyaniline (PANI) on carbon cloth (PANI/CC) is conducted through steps comprising using ammonium persulfate to polymerize aniline to form PANI on carbon cloth (CC), immersing clean CC in a 50 mL of mixture solution of 1 M H2SO4 and 0.55 mL aniline placed in an ice bath under magnetic stirring, adding 50 mL of 1 M H2SO4 containing 0.545 g ammonium persulfate dropwise to the mixture solution forming a reaction mixture; and placing the reaction mixture in the ice bath.
In another embodiment of the present invention, the reaction mixture is placed in the ice bath for 5 hours, and a subsequently obtained green color PANI deposited CC is washed with de-ionized (DI) water and acetone and dried overnight at 60° C. prior to further use.
In another embodiment of the present invention, preparation of Ni—Co4N@NC nanoparticles arrays on CC comprises the steps of growing PANI nanowires on a carbon cloth (CC) substrate through polymerization of aniline in a chilled environment resulting in PANI coated CC, growing NiCo precursor nanosheets on the PANI coated CC under a hydrothermal process, and calcinating the PANI coated CC in a tubular furnace under Ar/NH3 environment at 700° C.
In another embodiment of the present invention, formation of metal nitrides from the NiCo precursor nanosheets takes place inside the tubular furnace.
In another embodiment of the present invention, an SEM image of the prepared Ni—Co4N@NC nanoparticles arrays on CC reveals that the NiCo precursor nanosheets are assembled into uniformly oriented free-standing 1D nanorods and are perpendicularly anchored on the CC substrate, forming hierarchical arrays.
As another aspect of the present invention, a hybrid supercapacitor cell assembled by employing Ni—Co4N-2@NC as a positive electrode and AC as a negative electrode with a PVA (poly vinyl alcohol)/KOH as a gel electrolyte, is proposed.
In an embodiment of the present invention, the PVA-KOH gel electrolyte is prepared by the steps comprising dissolving 6 g of PVA was dissolved in 30 ml of de-ionized (DI) water under heating at 80° C. with continuous stirring until formation of a transparent solution, cooling the transparent solution, and adding 20 mL of 1 M KOH aqueous solution into the cooled transparent solution under continuous stirring until formation of a viscous solution.
In another embodiment of the present invention, hetero-atomic Ni—Co4N nanoparticles are laminated on a highly conductive nitrogen-doped carbon (NC) matrix on carbon cloth through in-situ nitridation.
In another embodiment of the present invention, Ni—Co4N@NC is used as a redox active material for supercapacitor cathode electrodes.
In another embodiment of the present invention, the hybrid super-capacitor cell is generated with hetero-atomic NiCo4N@NC nanoparticles on a Ni foam, and is used as positive material and activated carbon as negative electrode.
The subject matter that is regarded as the invention is particularly pointed out and distinctly claimed in the claims at the conclusion of the specification. The foregoing and other aspects, features, and advantages of the invention are apparent from the following detailed description taken in conjunction with the accompanying drawings in which:
The cycling stability of the i-Co4N-2@NC electrode was explored by repeating 10,000 charging-discharging cycles at a current density of 15 Ag−1. The resulting graph of capacity retention with cycle number is depicted in
The intercept of Nyquist plot to the real x-axis provides value of Rs, and the magnified Nyquist plots are presented in
To support the superiority of Ni—Co4N-2@NC electrode, ex situ scanning electron microscope (SEM) and x-ray diffraction analysis (XRD) measurements were performed after cycling. The SEM image of Ni—Co4N@NC is provided in
GCD profiles recorded at different voltage windows demonstrate non-linear shapes with linear enhancement in both charge and discharge times amid voltage window are shown in
The aspects of the utilization of hetero-atomic self-supported metal nitrides for high energy hybrid supercapacitor (HSC) cells, according to the present invention will be described in conjunction with
In accordance with the present invention, nitridation-induced in situ coupling of novel, highly-efficient Ni—Co4N nanoparticles entrenched in N-doped carbon matrix is performed via a facile pyrolysis of layered Ni—Co hydroxide decorated on PANI/CC—polyaniline (PANI) nanotubes on the basis of a carbon cloth (CC). Additionally, the nitrogenous gases released from the pyrolysis of PANI are innovatively used to encourage in-situ conversion of NiCo@PANI to Ni—Co4N@NC. The N-doped carbon network derived on CC forms a stable and highly conductive interconnected network. The prepared electrode possesses heteroatoms, which enrich electrochemically active sites and thereby electrochemical performance. Benefiting from all these promising features, the resultant Ni—Co4N@NC electrode shows exceptionally high electrochemical performance for supercapacitors. Furthermore, the HSCs cell constructed with Ni—Co4N@NC and activated carbon (AC) as cathode and anode, respectively demonstrates specific energy of 57.2 Wh kg−1 at a specific power of 843.8 W kg−1 and capacity retention of 89.7% after 15,000 cycles.
The self-supported integrated structure of electrode consisting of heteroatoms is advantageous for high performance energy storage applications. In accordance with the present invention, hetero-atomic Ni—Co4N nanoparticles laminated on highly conductive nitrogen-doped carbon (NC) matrix are developed through in-situ nitridation (a process that results in the formation of nitrides in a material) for high energy and stable hybrid super-capacitor (HSC). The plenty of available and rendering electrochemically active sites, specifically, single atom Ni, Co4N nanoparticles, hetero-atomic N-doped carbon matrix, and their several synergistic effects facilitate fast electron transfer and superior electrochemical performance. Benefiting from these merits, the resultant Ni—Co4N@NC electrode demonstrates robust electrochemical activity with high specific capacity of 397.5 mA h g−1, high rate capability of 72.4% and superior cycling stability over 10,000 cycles. The hetero-atomic Ni—Co4N@NC electrode is further employed for the HSC cell beside with the activated carbon (AC) electrode, which establishes a specific energy of 57.2 Wh kg−1 at a specific power of 843.8 W kg−1 and cyclic stability of 89.7% after 15,000 cycles. The present invention highlights the utilization of hetero-atomic self-supported metal nitrides for the high energy HSCs cell, paving the way to the expansion of highly efficient electrode materials for the future energy storage systems.
Considering experimental details pertaining to the present invention, the below mentioned chemicals are analytical grade and used as received without further purification. Ammonium persulfate ((NH4)2S2O8), aniline, cobalt nitrate hexahydrate (Co(NO3)2·6H2O), nickel nitrate hexahydrate (Ni(NO3)2·6H2O), ammonium fluoride (NH4F), urea (CO(NH2)2), potassium hydroxide (KOH), hydrochloric acid (HCl), activated carbon (AC), carbon black, polyvinylidene fluoride (PVDF) have been used for conducting experiments, in accordance with the present invention. In an embodiment of the present invention, the synthesis of polyaniline (PANI) on carbon cloth (PANI/CC) is conducted, wherein ammonium persulfate was used to polymerize aniline to form PANI on carbon cloth (CC). The well cleaned CC (2 cm×3 cm) was immersed in a 50 mL of mixture solution of 1 M H2SO4 and 0.55 mL aniline placed in an ice bath under magnetic stirring. 50 mL of 1 M H2SO4 containing 0.545 g ammonium persulfate was added dropwise to the above mixture solution. Later, the reaction mixture was placed for 5 hours in the same ice bath. After the reaction, obtained green color PANI deposited CC was washed several times with de-ionized (DI) water and acetone and dried overnight at 60° C. prior to further use.
In another embodiment of the present invention, the synthesis of nickel cobalt precursors on PANI/CC (NiCo@PANI/CC) is conducted. In a typical synthesis, the reaction solution was prepared by adding 0.05M Ni(NO3)2·6H2O, 0.1M Co(NO3)2·6H2O, 0.25M NH4F and 0.5M CO(NH2)2 in 40 mL of DI water. The solution was poured into the Teflon lined stainless-steel autoclave. The piece of PANI/CC (2 cm×3 cm) was immersed into the Teflon liner and autoclave was subjected to hydrothermal treatment at 120° C. for 12 hours. After the autoclave cooled down to room temperature, NiCo@PANI/CC was removed and washed thoroughly with DI water and acetone and dried at 60° C. overnight. In another embodiment, the synthesis of nickel-cobalt nitride and nitrogen-doped carbon on carbon cloth (Ni—Co4N@NC/CC) is conducted. The Ni—Co4N@NC was prepared through the calcination of NiCo@PANI/CC precursor. In a typical synthesis, the prepared NiCo@PANI/CC substrate was subjected for thermal treatment in a tubular furnace at 700° C. for 2 hours at the heating rate of 5° C./min under a mixture of Ar/NH3 (50 sccm) flow, subsequent to which the sample was allowed to cool naturally at room temperature.
Nitridation is one of the most effective processes to prepare specific metal nitrides for various applications including catalysis, batteries and supercapacitors. Heteroatomic Ni—Co4N@NC nanoparticles arrays are successfully prepared through the nitridation of NiCo hydroxides developed on PANI covered CC. A facile scheme and steps involved in the preparation of Ni—Co4N@NC nanoparticles arrays on CC is schematically illustrated in
The microstructure of the obtained materials is analyzed using the scanning electron microscopy (SEM). SEM image for PANI shows that the CC substrate is densely coated by PANI nanowires, which are interconnected to each other. After the hydrothermal process, the PANI/CC substrate surface is fully covered by the dense growth of NiCo precursors. The SEM image reveals that the NiCo precursor nanosheets is assembled into uniformly oriented free-standing 1D nanorods and are perpendicularly anchored on the substrate surface, forming hierarchical arrays. Moreover, the phase structure of PANI/CC and Ni—Co hydroxide precursors are analogous to earlier reported literature which was confirmed by XRD characterization. Following the nitridation treatment, the Ni—Co/PANI precursor is converted into crystalline Ni—Co4N@NC nano-architecture. The Ni—Co4N@NC nano-architecture firmly anchored on the surface of CC, is shown in
The different lattice arrangements in Ni—Co4N@NC nanoparticles offer more surface-active sites for energy storage. Additionally, considering the scanning transmission electron microscopy energy dispersive X-ray spectroscopy (STEM-EDS) element mapping images of Ni—Co4N@NC nanoparticles arrays manifesting the consistent allotment of Ni, Co, C and N elements, and considering the morphology for other samples prepared by varying the molar ratios—there is almost no change in the surface morphology of Ni—Co4N-1@NC and Ni—Co4N-3@NC samples. The crystallographic arrangement of Ni—Co4N@NC was inspected with X-ray diffraction (XRD) study. The XRD pattern for Ni—Co4N@NC is depicted in
With the purpose of getting comprehensive updates corresponding to the chemical bonding states of elements in the obtained material, X-ray photoelectron spectroscopy (XPS) investigation was executed. The XPS broad scan spectrum of Ni—Co4N@NC clearly evidences for the occurrence of Ni, Co, N and C elements lacking other contaminants. The narrow scan XPS spectra of elements in Ni—Co4N@NC are presented in
Surprisingly, pyrolysis of PANI forms N-doped carbon matrix over the CC, which is further confirmed from C 1s and N 1s XPS spectra. The C is spectrum (
The energy storage performance of obtained materials as supercapacitor electrodes were measured in standard three-electrode setup with 1 M KOH as an electrolyte. Initially, CV (capacitance-voltage profiling) tests for all the prepared samples as electrodes were performed at an identical sweep rate of 100 mVs−1 in a potential window of 0-0.6 V (vs. Hg/HgO). The relative CV profiles for all the electrodes are depicted in
Further, in order to confirm the high supercapacitors performance of Ni—Co4N-2@NC, the specific capacity is evaluated and the obtained results are presented in
More importantly, the intercept of Nyquist plot to the real x-axis provides value of Rs. The magnified Nyquist plots are presented in
Considering the best electrochemical activity of Ni—Co4N-2@NC electrode, additional three-electrode tests were carried out to evaluate the rate capability, energy storage features and long-term cycling performance. To evaluate the rate performance and kinetics of Ni—Co4N-2@NC electrode—CV and GCD tests were executed at different sweep rates. The CV profiles for Ni—Co4N-2@NC recorded at sweep rates from 5 to 100 mVs−1 depicts fine redox peaks in both cathodic and anodic region, representing a good redox behaviour of the active material (
As clearly seen from
From the stability test, the Ni—Co4N-2@NC electrode maintains 93% of its preliminary capacity over 10,000 cycles, and the capacity retention obtained for Ni—Co4N-2@NC electrode is considerably superior to those of formerly reported metal nitride electrodes. Notably, the Coulombic efficiency of the electrode is very high (>98%), signifying the high reversibility of electrode during redox reactions. The schematics for the charge storage process of Ni—Co4N@NC electrode in a KOH electrolyte is depicted in
The excellent electrochemical activity of Ni—Co4N-2@NC electrode is endorsed to various aspects such as the unique structural design and synergistic effect between different heteroatoms provide numerous electrochemically active sites and ion diffusion pathways, the free-standing design of Ni—Co4N-2@NC nanoparticles arrays on the surface of CC minimizes the dead volume and resistance arising from the additives, thereby enhancing the conductivity and energy storage capacity of the electrode. Further, the vertically aligned nanoparticles composed nanorods provide lots of electroactive sites as well as superhighways for the electron transport and the development of nitrides recompense the electronic states of the Ni—Co4N-2@NC electrode which enhances the conductivity and overall performance of the supercapacitors.
Considering electrochemical performance of hybrid solid-state supercapacitor (HSC) cells, hybrid-type of supercapacitors offer both high energy as well as high power. In order to illustrate the feasibility of the proposed Ni—Co4N-2@NC electrode towards practical applications, hybrid supercapacitor cells are assembled by employing Ni—Co4N-2@NC as a positive electrode and AC as a negative electrode with a PVA (poly vinyl alcohol)/KOH as the gel electrolyte. The schematics of the as constructed Ni—Co4N-2@NC//AC HSC cells are illustrated in
The PVA-KOH gel electrolyte was prepared according to the following procedure: Initially 6 g of PVA was dissolved in 30 ml of DI water under heating at 80° C. with continuous stirring until the formation of clear transparent solution. The gel solution was allowed to cool at ambient temperature naturally. Subsequently, 20 mL of 1 M KOH aqueous solution was dropped into the cooled gel solution under continuous stirring until the formation of transparent, viscous solution. To prepare solid-state device, firstly, the anode electrode was synthesized by mixing commercial activate carbon (AC), carbon black and PVDF in a mass ratio of 80:10:10. The slurry was prepared adding few drops of ethanol. Later the slurry was coated on Cu foam, which works as an anode, while the Cu3N/Ni3N electrode was directly applied as a cathode. The thin layer of PVA-KOH gel electrolyte was applied over both the electrodes and accumulated face to face through a mild griping and then covered with a parafilm.
The optimal mass ratio between the positive and negative electrode was obtained using the charge balance (Q+=Q−) denoted in equation:
where, m, C and V are the mass, capacitance and the potential window for the positive and negative electrode. The calculated mass ration from the positive to negative electrode is 1:1.56. The specific capacitance (Csc, F g−1), specific energy (E, W h kg−1), and specific power (P, W kg−1) of the HSSC device were calculated using the following equations:
The specific energy and specific power are two significant components used to appraise the electrochemical feature of SCs for its real-world application. The specific energy and specific power for the Ni—Co4N-2@NC//AC HSC cells were explored from the capacitance of whole HSC cells. The HSC cells delivers a favourable specific energy of 57.2 Wh kg−1 at a specific power of 843.8 W kg−1 and maintained a specific energy of 32.8 Wh kg−1 at high specific power of 8437.5 W kg−1. The prepared HSC cell is capable to distribute together high energy with high power. Surprisingly, the high specific energy and power achieved for Ni—Co4N-2@NC//AC HSC cell is significantly beyond to those of reported asymmetric and HSCs devices, for example Ni—NiWO4//NiS/NS—C (43.68 W h kg at 0.85 kW kg−1)43 CoO@C//reduced graphene oxide (RGO) (43.99 Wh kg at 824.8 Wkg)39, Ni3N@RGO//DEG@RGO (50.5 Whkg−1 at 800 W kg−1)44, NCF—N@FG//NF-3/500° C./CKK membrane//AC@NF (56.3 W h kg−1 at 374.6 W kg−1)45, Zn—Co—Se//Graphene-ink (16.97 W h kg−1 at 539.63 W kg−1)46, ZnO@C@NiO//Graphene (35.7 W h kg−1 at 380.9 W kg−1)47. The cycling stability of Ni—Co4N-2@NC//AC HSC cell was measured at 5 A g−1 current density for 15,000 non-stop charging-discharging cycles. The HSCs cell retained 89.7% of its preliminary capacity over 15,000 cycles, indicating the outstanding cycling stability.
The linear increase in capacitance and ˜100% coulombic efficiency indicates the excellent energy storage performance and good reversibility between active electrodes. The rate capability is important for practical function of SCs to know its performance at each sweep rates, and in order to estimate the rate capability, CV and GCD tests were carried out at various sweep rates and current densities. The CV profiles for Ni—Co4N-2@NC/AC HSC cells measured at sweep rates ranging from 5 to 150 mVs−1 in a voltage range of 0-1.6 V, as presented in
In another embodiment of the present invention, the HSC cells achieved highest specific capacitance of 183 Fg−1 at 1 Ag−1 and further maintained to 105 Fg−1 at 10 Ag−1, respectively. Notably, Ni—Co4N-2@NC/AC HSC cells achieved rate capability of 57.4%. The specific energy and specific power are two significant components used to appraise the electrochemical feature of supercapacitors for its real-world application. The specific energy and specific power for the Ni—Co4N-2@NC/AC HSC cells were explored from the capacitance of whole HSC cells and presented as the Ragone plot in
Furthermore, EIS analysis performed for Ni—Co4N-2@NC//AC HSC cells exhibits the very low Rs of 1.31 Ωcm−2 with small Rct of 0.07 Ωcm−2, representing the fast reaction kinetics between active electrode and electrolyte (
In another embodiment of the present invention, the present approach may be upgraded for different nanomaterials and their commercialization for advanced energy storage devices. The invention discloses novel self-supported hetero-atomic electrode composed of Ni—Co4N@NC stacked-nanoparticles confined in highly conductive nitrogen-doped carbon (NC) matrix through in-situ nitridation for high energy and stable HSCs. The integral design of stacked nanoparticles anchored on highly conductive nitrogen-doped carbon substrate offers fast charge transport as well as increases the exposed surface-active sites. With high electrical conductivity and heteroatom structure benefits, the resulting Ni—Co4N@NC electrode yields a maximum specific capacity of 397.5 mA h g−1 at current density of 1 A g−1 with a superb rate capability of 72.4% and better cycling stability after 10,000 charge-discharge cycles. Also, the proposed HSC cells are constructed using Ni—Co4N-2@NC and AC electrodes. The resultant HSC cells demonstrate excellent electrochemical performance bringing a specific energy of 57.2 Wh kg−1 at a specific power of 843.8 W kg−1 and long-term cycling stability after 15,000 cycles with capacity retention of 89.7%.
In the search of clean and highly efficient energy storage systems, hybrid supercapacitors (HSCs) are one of the best choices owing to their ultrahigh power densities along with stable cycling performance, cost-effectiveness, high efficiency and being environment friendly. However, the surface controlled electrochemical reactions of the supercapacitors restricts the charge transfer process on or near surface leading to relatively inferior energy storing capacity than the present Li-ion batteries (LIBs), which hampers their leading role in practical devices. Hybrid design of supercapacitors assembled with the redox active positive electrode and carbon composed negative electrode can be able to tackle the low energy density limit exclusive of surrendering power density and cycle life. Hence, it is necessary to design and develop novel redox active positive electrode materials to fabricate the HSCs with high energy density. In the present invention, nitridation-induced in situ coupling of novel, highly-efficient Ni—Co4N nanoparticles entrenched in N-doped carbon (NC) matrix is successfully developed via a facile pyrolysis of layered Ni—Co hydroxide decorated on PANI/CC. The Ni—Co4N@NC material is effectively used as a redox active material for supercapacitor cathode electrode.
The in-situ growth of cathode electrode (Ni—Co4N@NC nanoparticles on carbon cloth has several advantages, such as the presence of interstitial nitrogen in the electronic structure of cobalt unit cell facilitates quick electron transfer and thereby offers high electrical conductivity, high intrinsic activity, and stable performance. Further, the carbon atoms from the carbon matrix are replaced with the doped N atoms and the charge transfer takes place between adjacent carbon atoms and doped N atoms, which enhances the conductivity and create more active sites for electrochemical activity of the electrode. Further, availability of plenty of rendering electrochemically active sites, specifically, single-atom Ni, Co4N nanoparticles, and hetero-atomic N-doped carbon matrix, and their several synergistic effects facilitate fast electron transfer and provide abundant electroactive sites for rapid redox reactions. The free-standing design of Ni—Co4N-2@NC nanoparticles arrays on the surface of CC minimizes the dead volume and resistance arising from the additives, thereby enhancing the conductivity and energy storage capacity of the electrode. The vertically aligned nanoparticles composed nanorods provide lots of electroactive sites as well as superhighways for the electron transport. As a result, excellent electrochemical properties are obtained, such as specific capacities of 397.5 mA h g−1 at 1 A g−1 and high-rate capability of 72.4% and a remarkable cycling stability of 93% over 10000 cycles and Coulombic efficiency (>98%).
In addition, for the first time, heteroatomic Ni—Co4N nanoparticles are laminated on highly conductive nitrogen-doped carbon (NC) matrix on carbon cloth through in-situ nitridation. Nitridation is one of the best effective processes to prepare specific metal nitrides for various applications. This method has several advantages, such as PANI nanowires are grown on CC substrate through the simple polymerization of aniline in a chilled environment. The PANI afford additional NH3 gas throughout pyrolysis as well as resulting in the formation of N-doped carbon matrix between active material and CC substrate. Further, the process is very simple, cost-effective compared with other methods and can be used for large area deposition. As another aspect of the present invention, a hybrid supercapacitor (HSC) cell is fabricated using the heteroatomic Ni—Co4N@NC electrode beside the activated carbon (AC) electrode. The fabricated HSC cell is found to exhibit excellent performance features such as large operating potential window of 1.5 V, amazing specific energy of 57.2 Wh kg−1 at a specific power of 843.8 W kg−1 and a superior cycling stability of 89.7% after 15,000 cycles with 100% of columbic efficiency.
In another embodiment of the present invention, a hybrid super-capacitor (HSC) cell generated with the hetero-atomic NiCo4N@NC nanoparticles on Ni foam is used as positive material and activated carbon as negative electrode, and the resultant HSC cell has the following performance features such as a large operating potential window, high specific energy at a given specific power and a superior cycling stability with 100% columbic efficiency. The obtained results are classified into two categories namely, the fabrication of self-supported hetero-atomic electrode composed of Ni—Co4N@NC stacked-nanoparticles confined in highly conductive nitrogen-doped carbon (NC) matrix through in-situ nitridation and the construction of a HSC cell based on the Ni—Co4N@NC nanoparticles on Ni foam and AC electrodes.
The surface morphology of prepared samples was analyzed using a field emission scanning electron microscopy (FESEM, JEOL-7800F) and a transmission electron microscopy (TEM, JEOL JEM-2010). The structural analysis of the prepared samples were performed by the X-ray diffraction (XRD) analysis (Rigaku diffractometer (Maxima XRD-7000) using Cu K alpha radiation (λ=1.5406 A.U.)). The oxidation states of the elements present in the prepared sample were investigated by X-ray photo-electron spectrometry (XPS) measurements (XPS, Thermo Scientific Inc. UK with monochromatic Al Kα X-rays). The electrochemical performances were measured using a electrochemical workstation (ZIVE SP2) in a typical three-electrode setup. For the three-electrode configuration, prepared materials were directly used as working electrodes (1 cm2), platinum wire was used as counter electrode, Hg/HgO was used as reference electrode and 1 M KOH aqueous solution as an electrolyte. The electrochemical performances were tested using cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) measurements recorded at different scan rates and current densities, respectively. The electrochemical impedance spectroscopy (EIS) analysis was performed at frequency ranges from 100 kHz to 0.01 Hz at applied voltage of 10 mV.
The specific capacity (Qs) and areal capacitance (CA) were calculated from the discharge curve using the following formulae: QS=(I×Δt)/(m×3.6) and CA=(I×Δt)/(A×ΔV), where, I (A) represents the discharge current density, Δt (s) represents the discharge time, m (g) is the mass of active material, ΔV is the voltage window and A (cm2) is the area of active electrode material.
Hybrid design of supercapacitors includes redox active positive electrode assembled with carbon composed negative electrode, which gives high energy density, facile pyrolysis of layered Ni—Co hydroxide decorated on PANI/CC produces Ni—Co4N nanoparticles entrenched in N-doped carbon (NC) matrix (NiCo4N@NC) and nitrogenous gases released from pyrolysis of PANI used to encourage in situ conversion of Ni—Co hydroxide@PANI to Ni—Co4N@NC. N-doped carbon derived on CC forms a stable, highly conductive interconnected network and the resultant NiCo4N@NC electrode has high electrochemical performance for supercapacitors. NiCo4N@NC is used as a redox active material for the supercapacitor cathode (cathode electrode being NiCo4N@NC nanoparticles on carbon cloth). The hybrid super-capacitor (HSC) cell generated with the hetero-atomic NiCo4N@NC nanoparticles on Ni foam used as positive material and activated carbon as negative electrode. The plenty of rendering electrochemically active sites, specifically, single-atom Ni, Co4N nanoparticles, and hetero-atomic N-doped carbon matrix, and their several synergistic effects facilitate fast electron transfer and superior electrochemical performance. The free-standing design of Ni—Co4N-2@NC nanoparticles arrays on the surface of CC minimizes the dead volume and resistance arising from the additives, thereby enhancing the conductivity and energy storage capacity of the electrode. The vertically aligned nanoparticles composed nanorods provide lots of electroactive sites as well as superhighways for the electron transport, and the development of nitrides recompenses the electronic states of Ni—Co4N-2@NC electrode which enhances the conductivity and overall supercapacitor performance.
Many changes, modifications, variations and other uses and applications of the subject invention will become apparent to those skilled in the art after considering this specification and the accompanying drawings, which disclose the preferred embodiments thereof. All such changes, modifications, variations and other uses and applications, which do not depart from the spirit and scope of the invention, are deemed to be covered by the invention, which is to be limited only by the claims which follow.