CN108962632B - Preparation method of graphene/nitrogen-doped carbon/nickel oxide composite material - Google Patents
Preparation method of graphene/nitrogen-doped carbon/nickel oxide composite material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention belongs to the technical field of energy storage materials, and relates to a preparation method of a graphene/nitrogen-doped carbon/nickel oxide composite material, which is used for the preparation occasion of a supercapacitor electrode material and solves the problems of more preparation steps, long time consumption and low specific capacitance of a composite and is not beneficial to material application in the traditional process, reduced graphene oxide/crosslinked polyacrylamide/nickel salt aerogel is adopted as a precursor, and the method is calcined to realize carbon material in-situ nitrogen doping, carbon thermal reduction and catalytic graphitization and compound the reduced graphene oxide to form a three-dimensional structure graphene/nitrogen-doped carbon/nickel oxide quaternary nano composite material, has simple preparation process and reliable principle, has lower equivalent resistance, interface charge transfer resistance and Warburg impedance as the supercapacitor electrode material, and has high specific capacitance of a product, the electrochemical performance is excellent, and the method has good economic benefit and application prospect.
Description
The technical field is as follows:
the invention belongs to the technical field of energy storage materials, and relates to a preparation method of a graphene/nitrogen-doped carbon/nickel oxide composite material (RGO/NPGC/Ni/NiO), wherein a product can be used in a super capacitor electrode material preparation occasion.
Background art:
the super capacitor has the advantages of high power density, quick charge and discharge, long cycle life, high efficiency, cleanness, safety and the like. Supercapacitors can be divided into electric double layer capacitors and faraday pseudocapacitors, depending on the energy storage mechanism. The electric double layer capacitor stores energy using an interfacial electric double layer between an electrode and an electrolyte, and occurs through a physical adsorption process, which generally employs activated carbon, graphene, or the like having a high specific surface area as an electrode material. Faraday pseudocapacitors produce higher specific capacities by undergoing rapid, reversible oxidation/reduction reactions (or chemisorption/desorption) in the electrode surface or near-surface bulk phase, with electrode materials consisting essentially of transition metal oxides, metal hydroxides, and conductive polymers. The design and construction of three-dimensional structure nanometer composite electrode materials by combining the double electric layer capacitance and the Faraday pseudo capacitance become development trends in the field of super capacitors.
The three-dimensional structure can promote the contact of electrolyte and electrode materials, and the high specific surface area and pore volume are beneficial to improving the power density and energy density of the materials. In order to enhance the performance of the electrode material of the supercapacitor, people also prepare a nitrogen atom doped carbon material. Lin et al use mesoporous silica as template, metal nickel as catalyst, methane and ammonia gas as gas source, and prepare nitrogen-doped thin carbon by chemical vapor deposition (Science,2015,350,1508). Among them, pyrrole-type nitrogen and pyridine-type nitrogen can impart oxidation-reduction activity and pseudocapacitance characteristics to the electrode material, and graphitized nitrogen contributes to improvement of conductivity of the carbon material. However, the chemical vapor deposition requires special equipment, and the preparation and removal of the template and the catalyst increase the reaction steps and increase the economic cost, which is not favorable for practical application.
Recently, the direct use of nitrogen-containing polymers such as chitosan and polyacrylamide as precursors for the preparation of nitrogen-doped carbon and its composites has received much attention. The polyacrylamide is a water-soluble polymer, the solution can be prepared without regulating and controlling the pH value of the solution, and the operation is simple and convenient. Chen et al prepared nitrogen-doped hierarchical porous carbon (ind. eng. chem. res.,2013,52,12025) using calcium acetate as a template and polyacrylamide as a precursor. The Chinese invention patent (publication No. CN107768645A) discloses a porous nitrogen-doped carbon nano-sheet composite negative electrode material and a preparation method thereof, wherein a polyacrylamide solution is used as a precursor, compounded with iron salt and calcined in inert atmosphere to generate Fe4N/Fe2O3The Fe porous nitrogen-doped carbon nanosheet is used as a lithium ion battery cathode material. The preparation of nitrogen-doped carbon and the composite material thereof by adopting the polyacrylamide is simple and convenient to operate, and the nitrogen doping is more uniform. However, the organic precursor is often accompanied by glass transition and structural collapse during the thermal decomposition process, and the three-dimensional network structure of the polymer is difficult to maintain, which is also the reason why researchers often adopt templates to regulate the structure of the product when preparing porous materials. An effective way to obtain the three-dimensional nitrogen-doped carbon composite material is to adopt cross-linked polyacrylamide/nickel salt composite gel as a precursor and a self-template to regulate and control the preparation of the three-dimensional nitrogen-doped carbon/transition metal oxide composite electrode material, and no relevant research is recorded in documents at present.
The graphene has high conductivity and good stability, can promote charge transmission by being compounded with the oxide, and can effectively inhibit the aggregation and compounding of oxide nanoparticlesThe material has better electrochemical performance. Co produced by Deng et al3O4The specific capacity of the/three-dimensional graphene/foamed nickel composite material is 321F/g (J.Alloys Comp.,2017,693,16) under the current density of 1A/g. Wei et al prepared a graphene oxide/nickel oxide composite and reduced the graphene oxide/nickel oxide nanocomposite by hydrogen reduction to form a three-dimensional flower-like shape, the product had good conductivity, porosity and stability, and when the current density was 0.38A/g, the specific capacitance of the composite reached 428F/g (Energy)&Fuels,2013,27, 6304). Recently, scientists have also studied composites of metal nanoparticles with carbon, Ding et al prepared a nickel/carbon composite at 50mA/cm2The specific capacitance of the carbon material under the condition is 174.5F/g, which is 2.49 times of that of the pure carbon material. (mater. lett.,2015,146, 20). Experimental results show that the graphene and metal nanoparticles can enhance the conductivity of the composite electrode material, improve the rate characteristic, promote charge transfer and improve the specific capacitance.
The preparation method has important significance for improving the performance of the electrode material of the super capacitor by taking the graphene, the cross-linked polyacrylamide and the transition metal salt as precursors to prepare the graphene/nitrogen-doped carbon/metal oxide compound with the three-dimensional structure. To date, there is no literature report of preparing composite electrode materials from graphene-containing crosslinked polyacrylamide gel systems. The research fully utilizes the crosslinked polymer gel as a precursor and a self-template to prepare the composite material with a three-dimensional structure in the preparation method, has simple and convenient operation, low cost and environmental protection, and belongs to a simple, convenient, efficient and novel method for preparing the composite material; the prepared material has the characteristics of high specific surface area of a porous carbon material, high conductivity of graphene and metal nanoparticles and high redox activity of a transition metal oxide, and the product has excellent electrochemical performance and wide application prospects in the fields of energy storage, catalysis and the like.
The invention content is as follows:
the invention aims to overcome the defects of the existing synthesis technology, provides a preparation method of a three-dimensional graphene/nitrogen-doped carbon/nickel oxide nano composite material, solves the problems of more process preparation steps, long time consumption, low specific capacitance of a composite and unfavorable material application, and can simply, conveniently and efficiently prepare a supercapacitor composite electrode material.
In order to achieve the above object, the preparation method of the three-dimensional graphene/nitrogen-doped carbon/nickel oxide nanocomposite material according to the present invention comprises the steps of adding a phenolic crosslinking agent and an ascorbic acid reducing agent into a graphene oxide/polyacrylamide/nickel salt aqueous solution, forming a reduced graphene oxide/crosslinked polyacrylamide/nickel salt hydrogel under a hydrothermal condition, performing liquid nitrogen rapid freezing and freeze-drying treatment to form a reduced graphene oxide/crosslinked polyacrylamide/nickel salt three-dimensional aerogel, calcining a sample to form a three-dimensional graphene/nitrogen-doped carbon/nickel oxide nanocomposite material, and performing a specific process comprising the following steps:
(1) preparing Graphene Oxide (GO): 1.0g of graphite powder was weighed into a 250mL three-necked flask, ice-washed, and 46.0mL of concentrated sulfuric acid (98 wt%) and 1.0g of NaNO were added3And stirring for 30 min. Then 6.0g KMnO was slowly added4The temperature is raised to 35 ℃ and the mixture is stirred for 2 hours. And (3) slowly adding 15.0mL of deionized water into the three-neck flask, stirring for 15min, stopping heating, adding 200.0mL of deionized water and 20.0mL of hydrogen peroxide, changing the solution from purple red to bright yellow, and stopping reaction. The centrifugation was washed 3 times with dilute hydrochloric acid (5 wt%) and extensively dialyzed to neutrality with copious amounts of deionized water to give a tan GO solution. And (5) carrying out ultrasonic treatment for 2h for standby.
(2) Preparing a polymer solution containing graphene oxide: dissolving polyacrylamide in deionized water to prepare a polymer solution with the mass percentage concentration of 0.5-3%; adding a graphene oxide aqueous solution, controlling the concentration of the graphene oxide in the polymer solution to be 0.6-1.0mg/mL, and uniformly stirring;
(3) adding a transition metal salt: adding nickel salt into the solution, fully stirring for 0.5h to completely dissolve the nickel salt, wherein the concentration of nickel ions in the solution is 0.05-0.20 mol/L;
(4) adding a cross-linking agent and a reducing agent: adding a phenolic crosslinking agent into the prepared polymer aqueous solution, wherein the amount ratio of the amide group to the phenolic compound substance is 5-10, and the amount ratio of the formaldehyde to the resorcinol substance is 2-6; adding ascorbic acid into the solution as a reducing agent of the graphene oxide, controlling the mass ratio of the graphene oxide to the ascorbic acid to be 1:4, and fully stirring for 0.5h to completely dissolve the graphene oxide and the ascorbic acid;
(5) adding a pH regulator: then, 50-400 mu L of hydrochloric acid (3mol/L) is dripped into the solution and is evenly stirred, and the pH value of the solution is adjusted to be within the range of 3.0-6.5;
(6) preparing Reduced Graphene Oxide (RGO)/crosslinked polyacrylamide/nickel salt composite hydrogel: transferring the solution to a pressure kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 8-15h at the temperature of 100-150 ℃ to obtain reduced graphene oxide/crosslinked polyacrylamide/nickel salt composite hydrogel, and naturally cooling to room temperature;
(7) preparing reduced graphene oxide/crosslinked polyacrylamide/nickel salt composite aerogel: freezing the composite hydrogel for 0.5h at low temperature (-196 ℃) of liquid nitrogen, and drying the composite hydrogel for 8-24h in a freeze dryer to obtain the reduced graphene oxide/crosslinked polyacrylamide/nickel salt composite aerogel;
(8) sample calcination: putting the aerogel prepared in the step (7) into a porcelain boat, putting the porcelain boat into a quartz tube furnace, and adjusting the nitrogen flow to be 150cm3Min, aeration for 0.5h to remove air from the tube furnace, then nitrogen flow was adjusted to 50cm3And/min, heating to 600-inch sand 900 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 2h, then closing the heat source, carbonizing the organic component at high temperature, simultaneously realizing in-situ nitrogen doping, carrying out carbothermic reduction on nickel salt to generate a nickel simple substance, carrying out catalytic graphitization conversion on amorphous carbon by using metallic nickel to form a partially graphitized structure, cooling the tubular furnace to room temperature, closing the nitrogen source, heating to 250 ℃ at the heating rate of 5 ℃/min in the air atmosphere for promoting nickel element oxidation, and keeping the temperature for 10h, thereby realizing the preparation of the reduced graphene oxide/nitrogen-doped partially graphitized carbon/nickel oxide quaternary nanocomposite.
The polyacrylamide in the step (2) is any one of unhydrolyzed polyacrylamide and partially hydrolyzed polyacrylamide (the degree of hydrolysis is 5-25%).
The nickel salt in the step (3) is any one of nickel chloride and nickel nitrate.
In the step (4), the phenolic aldehyde crosslinking agent is any one of phenol-formaldehyde and resorcinol-formaldehyde.
Graphene/nitrogen doped carbon/nickel with three-dimensional structureThe method for preparing the working electrode by taking/nickel oxide nano composite material (RGO/NPGC/Ni/NiO) as the electrode material of the super capacitor comprises the following specific steps: firstly, sampling 50-100mg of RGO/NPGC/Ni/NiO, a conductive agent acetylene black and a binder according to the mass ratio of 80:10:10, wherein the binder is polytetrafluoroethylene emulsion with the mass percentage concentration of 5%, then using 0.5-2.0mL of N-methyl pyrrolidone (NMP) for size mixing, coating the mixture on a foamed nickel current collector with the thickness of 1cm multiplied by 1cm, placing the foamed nickel current collector in an oven for drying for 2h at the temperature of 70 ℃, then drying for 12h under the vacuum condition of 100 ℃ to completely remove the NMP, calculating the loading capacity of the RGO/NPGC/Ni/NiO according to the mass change before and after the foamed nickel coating the slurry, and controlling the loading capacity to be 0.8-1.0mg/cm2. A three-electrode system is constructed by using a prepared working electrode, a saturated calomel electrode SCE and a platinum sheet (1cm multiplied by 2cm), an electrochemical test is carried out in 6mol/L KOH solution, wherein the Saturated Calomel Electrode (SCE) is a reference electrode, the platinum sheet is a counter electrode, a CHI660D electrochemical workstation is adopted for carrying out Cyclic Voltammetry (CV) scanning, constant current charging and discharging (GCD) test and alternating current impedance spectroscopy (EIS) analysis, the voltage range of the CV and GCD test is 0-0.4V vs. SCE, the CV test control scanning rate is 5mV/s, the GCD test control current density is 1-10A/g, the specific capacitance of a product is calculated, and the multiplying power characteristic of the product is inspected. The specific capacitance calculation formula in the discharging process is as follows:
wherein C is specific capacitance, F/g; i represents charge-discharge current, A; Δ t is the discharge time, s; m is the mass of the active material on the working electrode, g; Δ U is the total voltage drop, V. Alternating current impedance spectroscopy (EIS) test frequency range 10-2-105Hz, amplitude 5 mV.
Compared with the prior art, the method takes the graphene oxide and the nitrogen-containing high-molecular polyacrylamide as reaction precursors, the reaction precursors are subjected to crosslinking reaction with a phenolic compound and are compounded with inorganic nickel salt, and the reduced graphene oxide/crosslinked polyacrylamide/nickel salt three-dimensional aerogel is formed after freezing and drying treatment, wherein the polymer crosslinked network structure can enhance the stability of the organic precursor in the calcining process and endow the product with a three-dimensional hierarchical porous structure, and the graphene is beneficial to improving the conductivity and the number of active sites of the material. The preparation method combines multiple functions of in-situ nitrogen doping, catalytic graphitization, self-template regulation and the like into a whole, the specific surface area of the material can be improved by the three-dimensional porous structure, the conductivity of the metal and graphitized carbon structure can be enhanced, and the pseudo-capacitance characteristic of the composite material can be improved by the nitrogen doping and the transition metal oxide. The preparation method does not involve extra template introduction and removal, so that the preparation process has the advantages of simple steps, energy conservation, environmental protection, reliable principle and low production cost. The composite material keeps the three-dimensional structure of the crosslinked polymer precursor, is beneficial to full contact of electrolyte and electrode materials, has good conductivity and sufficient redox active sites, has the double electric layer capacitance characteristic and the pseudocapacitance characteristic, has higher specific capacitance, good multiplying power characteristic and cycle stability, and has wide application prospect in the field of super capacitors.
Description of the drawings:
FIG. 1 is an X-ray diffraction pattern of an RGO/NPGC/Ni/NiO composite prepared according to the present invention.
FIG. 2 is a scanning electron micrograph of the graphene oxide (a) and the RGO/NPGC/Ni/NiO composite (b) prepared by the method.
FIG. 3 is a cyclic voltammogram of an RGO/NPGC/Ni/NiO series composite and an NPGC/Ni/NiO composite prepared by the present invention.
FIG. 4 is the constant current charge and discharge curves of the RGO/NPGC/Ni/NiO series composite and the NPGC/Ni/NiO composite prepared by the present invention.
FIG. 5 is a charge-discharge curve and rate characteristic curve of RGO (0.8)/NPGC/Ni/NiO composite prepared by the present invention under different current densities.
FIG. 6 is an AC impedance spectrum of the RGO (0.8)/NPGC/Ni/NiO and NPGC/Ni/NiO composites prepared according to the present invention.
The specific implementation mode is as follows:
the following is a further description by way of example and with reference to the accompanying drawings.
Example 1:
30mL of polyacrylamide mother liquor (5 wt%) is diluted by 45mL of deionized water to form a uniform solution with the concentration of 2%, 4.5mL of graphene oxide mother liquor (10mg/mL) is dropwise added under the condition of strong stirring, and the concentration of graphene oxide in the solution is controlled to be 0.6 mg/mL. To the direction of464.4mg of resorcinol, 1.26mL of formaldehyde (37 wt%), 2.67g of NiCl were added to the solution2·6H2O and 300. mu.L hydrochloric acid (3mol/L), and 0.18g of ascorbic acid was added as a reducing agent for graphene oxide. And uniformly stirring the mixture solution, transferring the mixture solution into a 100mL pressure kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction at 130 ℃ for 15h to obtain the reduced graphene oxide/crosslinked polyacrylamide/nickel chloride hydrogel. And (3) rapidly freezing the gel by using liquid nitrogen, and drying the gel in a freeze dryer for 24 hours (the temperature is 50 ℃ below zero and the vacuum degree is 8Pa) to obtain the reduced graphene oxide/crosslinked polyacrylamide/nickel chloride composite aerogel. Placing the aerogel in a porcelain boat, placing in a quartz tube furnace at 150cm3Introducing nitrogen for 30min under the nitrogen flow, and discharging air in the pipe; the nitrogen flow was varied to 50cm3Heating to 800 ℃ at a heating rate of 1 ℃/min for min, keeping the temperature for 2h, and stopping heating. And after the sample is cooled to the room temperature, closing a nitrogen source, raising the temperature to 250 ℃ at the temperature rise rate of 5 ℃/min in the air atmosphere, and keeping the temperature for 10 hours to finally obtain the three-dimensional graphene/nitrogen-doped carbon/nickel oxide composite, which is marked as RGO (0.6)/NPGC/Ni/NiO.
Example 2:
30mL of polyacrylamide mother liquor (5 wt%) is diluted by 45mL of deionized water to form a uniform solution with the concentration of 2%, 6.0mL of graphene oxide mother liquor (10mg/mL) is dropwise added under the condition of strong stirring, and the concentration of graphene oxide in the solution is controlled to be 0.8 mg/mL. To the solution was added 464.4mg resorcinol, 1.26mL formaldehyde (37 wt%), 2.67g NiCl2·6H2O and 300. mu.L hydrochloric acid (3mol/L), and 0.24g of ascorbic acid was added as a reducing agent for graphene oxide. And uniformly stirring the mixture solution, transferring the mixture solution into a 100mL pressure kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction at 130 ℃ for 15h to obtain the reduced graphene oxide/crosslinked polyacrylamide/nickel chloride hydrogel. And (3) rapidly freezing the gel by using liquid nitrogen, and drying the gel in a freeze dryer for 24 hours (the temperature is 50 ℃ below zero and the vacuum degree is 8Pa) to obtain the reduced graphene oxide/crosslinked polyacrylamide/nickel chloride composite aerogel. Placing the aerogel in a porcelain boat, placing in a quartz tube furnace at 150cm3Introducing nitrogen for 30min under the nitrogen flow, and discharging air in the pipe; the nitrogen flow was varied to 50cm3/min，Heating to 800 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 2h, and then stopping heating. And after the sample is cooled to the room temperature, closing a nitrogen source, raising the temperature to 250 ℃ at the temperature rise rate of 5 ℃/min in the air atmosphere, and keeping the temperature for 10 hours to finally obtain the three-dimensional graphene/nitrogen-doped carbon/nickel oxide composite, which is marked as RGO (0.8)/NPGC/Ni/NiO.
Example 3:
30mL of polyacrylamide mother liquor (5 wt%) is diluted by 45mL of deionized water to form a uniform solution with the concentration of 2%, 7.5mL of graphene oxide mother liquor (10mg/mL) is dropwise added under the condition of strong stirring, and the concentration of graphene oxide in the solution is controlled to be 1.0 mg/mL. To the solution was added 464.4mg resorcinol, 1.26mL formaldehyde (37 wt%), 2.67g NiCl2·6H2O and 300. mu.L hydrochloric acid (3mol/L), and 0.30g of ascorbic acid was added as a reducing agent for graphene oxide. And uniformly stirring the mixture solution, transferring the mixture solution into a 100mL pressure kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction at 130 ℃ for 15h to obtain the reduced graphene oxide/crosslinked polyacrylamide/nickel chloride hydrogel. And (3) rapidly freezing the gel by using liquid nitrogen, and drying the gel in a freeze dryer for 24 hours (the temperature is 50 ℃ below zero and the vacuum degree is 8Pa) to obtain the reduced graphene oxide/crosslinked polyacrylamide/nickel chloride composite aerogel. Placing the aerogel in a porcelain boat, placing in a quartz tube furnace at 150cm3Introducing nitrogen for 30min under the nitrogen flow, and discharging air in the pipe; the nitrogen flow was varied to 50cm3Heating to 800 ℃ at a heating rate of 1 ℃/min for min, keeping the temperature for 2h, and stopping heating. And after the sample is cooled to the room temperature, closing a nitrogen source, raising the temperature to 250 ℃ at the temperature rise rate of 5 ℃/min in the air atmosphere, and keeping the temperature for 10 hours to finally obtain the three-dimensional graphene/nitrogen-doped carbon/nickel oxide composite, which is marked as RGO (1.0)/NPGC/Ni/NiO.
Comparative example 1:
30mL of polyacrylamide mother liquor (5 wt%) was diluted with 45mL of deionized water to form a homogeneous solution with a concentration of 2%. To the solution was added 464.4mg resorcinol, 1.26mL formaldehyde (37 wt%), 2.67g NiCl2·6H2O and 300. mu.L hydrochloric acid (3 mol/L). The mixture solution is stirred evenly and then transferred into a pressure kettle with 100mL of polytetrafluoroethylene lining for hydrothermal reaction for 15h at 130 ℃,to obtain the cross-linked polyacrylamide/nickel chloride hydrogel. And (3) rapidly freezing the gel by using liquid nitrogen, and drying the gel in a freeze dryer for 24 hours (the temperature is 50 ℃ below zero and the vacuum degree is 8Pa) to obtain the crosslinked polyacrylamide/nickel chloride composite aerogel. Placing the aerogel in a porcelain boat, placing in a quartz tube furnace at 150cm3Introducing nitrogen for 30min under the nitrogen flow, and discharging air in the pipe; the nitrogen flow was varied to 50cm3Heating to 800 ℃ at a heating rate of 1 ℃/min for min, keeping the temperature for 2h, and stopping heating. And after the sample is cooled to room temperature, closing a nitrogen source, heating to 250 ℃ at the heating rate of 5 ℃/min in the air atmosphere, and keeping the temperature for 10 hours to finally obtain the three-dimensional nitrogen-doped carbon/nickel oxide composite, which is recorded as NPGC/Ni/NiO.
FIG. 1 is an X-ray diffraction pattern of the RGO/NPGC/Ni/NiO composite prepared in example 2. As can be seen from the figure, the diffraction peaks of the compound at 37.3 degrees, 43.3 degrees and 62.9 degrees of 2 theta respectively correspond to the (111), (200) and (220) crystal plane diffraction of NiO (JCPDS: 65-5745); diffraction peaks appearing at 44.5 degrees, 51.8 degrees and 76.4 degrees of 2 theta respectively correspond to the (111), (200) and (220) crystal planes of Ni (JCPDS:65-2865), and the peak intensity of the simple substance Ni is greater than that of NiO, which indicates that the material contains a large amount of simple substance Ni and a small amount of NiO. The simple substance nickel has good conductivity, and is beneficial to the transfer of electrons; the nickel oxide has higher redox activity and can provide larger pseudocapacitance, and the combination of the nickel oxide and the pseudocapacitance can improve the electrochemical performance of the electrode material of the super capacitor. A broad peak was generated at 23.7 °, corresponding to the reduced graphene oxide (002) crystal plane diffraction peak, indicating that graphene oxide GO in the sample has been reduced to reduced graphene oxide RGO. Meanwhile, the transition metal Ni can also realize catalytic graphitization of the carbon skeleton in the material in the high-temperature calcination process. The graphitized structure is beneficial to improving the conductivity and stability of the electrode material in electrochemical reaction.
Fig. 2(a) is a scanning electron micrograph of GO, and it can be seen from the micrograph that GO prepared has a thin film-like structure. FIG. 2(b) is a scanning electron microscope image of RGO/NPGC/Ni/NiO material, in which the composite material maintains the three-dimensional network structure of the crosslinked polymer, and the inorganic nanoparticles are distributed in the carbon matrix and have uniform particle size. The C framework in the compound can enable the material to have a better three-dimensional structure, the electric double layer capacitance is increased, meanwhile, sites are provided for the growth of metal particles, the aggregation of the particles is prevented, the number of active sites can be increased, the conductivity of the material can be increased due to the graphene structure, the internal resistance of the material is reduced, and the transmission of electrons in the material is facilitated.
FIG. 3 is a plot of cyclic voltammograms for four samples of RGO (0.6)/NPGC/Ni/NiO, RGO (0.8)/NPGC/Ni/NiO, RGO (1.0)/NPGC/Ni/NiO and NPGC/Ni/NiO. As can be seen, the four samples all have distinct oxidation (0.25-0.27V) and reduction (0.13-0.14V) peaks at a scan rate of 5mV/s over the 0-0.4Vvs. SCE voltage range, indicating that the composite material has typical pseudocapacitive characteristics.
FIG. 4 shows the constant current charge and discharge curves at 2A/g current density for four samples, RGO (0.6)/NPGC/Ni/NiO, RGO (0.8)/NPGC/Ni/NiO, RGO (1.0)/NPGC/Ni/NiO and NPGC/Ni/NiO. As can be seen from the figure, each sample charge-discharge curve has a distinct discharge platform, which indicates that the material has a typical Faraday pseudocapacitance characteristic. Under constant current, the discharge time is in direct proportion to the specific capacitance value, and the specific capacitance values of the four samples are calculated to be 420.8, 444.0, 432.0 and 390.1F/g respectively. It is demonstrated that as GO concentration in the reaction precursor increases, the specific capacitance of the composite increases first and then decreases, which is probably because GO increases the number of active sites, which increases the specific surface area and conductivity of the calcined material; when the addition amount of GO is too high (1.0mg/mL), the carbon content of the generated compound is increased, the wall thickness is increased, the generated metal particles can be embedded in a carbon skeleton, active sites are reduced, and the generation of oxides and the subsequent electrochemical reaction in the tempering process are not facilitated. The experimental result shows that the NPGC/RGO (0.8)/Ni/NiO material has more excellent electrochemical performance.
FIG. 5(a) is a plot of constant current charge and discharge for the sample RGO (0.8)/NPGC/Ni/NiO at different current densities. As can be seen, the discharge time of the sample gradually decreases and the specific capacitance gradually decreases with increasing current density, and the specific capacitance is 511.5, 444.0, 412.8, 394.5 and 386.0F/g when the current density is 1, 2, 5, 8 and 10A/g respectively. Fig. 5(b) is a specific capacitance retention curve of RGO (0.8)/NPGC/Ni/NiO, and the specific capacitance retention rate of the sample decreases gradually as the current density increases, which may be because the partially graphitized carbon skeleton in the material may effectively improve the specific surface area and the conductivity of the material, increase the redox sites and the transfer rate of electrons inside the material, and reduce the specific capacitance attenuation at high current density to some extent. The specific capacitance retention of RGO (0.8)/NPGC/Ni/NiO was 75.5% at a current density of 10A/g. The composite material has good rate property as a super capacitor electrode material.
FIG. 6 is an AC impedance spectrum of RGO (0.8)/NPGC/Ni/NiO and NPGC/Ni/NiO samples. The Nyquist plots for both samples consist of a high frequency region semi-circular arc and a low frequency region diagonal line, and the intercept of the semi-circle and the Z' axis is the equivalent resistance (R) of the materialΩ) And the semi-circular arc diameter represents the interfacial charge transfer resistance (R) between the electrode and the electrolytect) The smaller diameter indicates faster charge transfer and better redox activity of the material, and the diagonal line represents the Warburg impedance (Z)w) The larger the slope, the faster the ions or electrons in the material diffuse, and the better the capacitance performance.
The ZSimpwin software is adopted to carry out data simulation analysis on the material alternating current impedance spectrum, the equivalent resistance of an RGO (0.8)/NPGC/Ni/NiO sample is only 0.40 omega, the interface charge transfer resistance is 0.79 omega, and the equivalent resistance is lower than that of a compound NPGC/Ni/NiO (the equivalent resistance is 0.46 omega, and the interface charge transfer resistance is 0.82 omega) without introducing a conductive agent, and meanwhile, the slope of the straight line of the former in a low-frequency region is higher. The results show that the RGO (0.8)/NPGC/Ni/NiO material has good conductivity, electrochemical activity and rich pore structure, and is a good supercapacitor electrode material.
The invention is not limited to the above description of the embodiments and should not be regarded as excluding other embodiments and being applicable to other combinations and modifications. Modifications and variations such as would occur to those skilled in the art are intended to be included within the scope of the appended claims without departing from the spirit and scope of the invention.
Claims (6)
1. A preparation method of a graphene/nitrogen-doped carbon/nickel oxide composite material is characterized by comprising the following specific preparation process steps:
(1) preparing a polymer solution containing graphene oxide: dissolving polyacrylamide in deionized water to prepare a polymer solution with the mass percentage concentration of 0.5-3%; adding a graphene oxide aqueous solution, controlling the concentration of the graphene oxide in the polymer solution to be 0.6-1.0mg/mL, and uniformly stirring;
(2) adding a transition metal salt: adding nickel salt into the solution, fully stirring for 0.5h to completely dissolve the nickel salt, wherein the concentration of nickel ions in the solution is 0.05-0.20 mol/L;
(3) adding a cross-linking agent and a reducing agent: adding a phenolic aldehyde crosslinking agent into the prepared polymer aqueous solution, wherein the amount ratio of the amide group to the phenolic compound substance is 5-10, and the amount ratio of the formaldehyde to the phenolic compound substance is 2-6; adding ascorbic acid into the solution as a reducing agent of the graphene oxide, controlling the mass ratio of the graphene oxide to the ascorbic acid to be 1:4, and fully stirring for 0.5h to completely dissolve the graphene oxide and the ascorbic acid;
(4) adding a pH regulator: then dropwise adding 3mol/L hydrochloric acid into the solution, uniformly stirring, and adjusting the pH value of the solution to be 3.0-6.5;
(5) preparing reduced graphene oxide/crosslinked polyacrylamide/nickel salt composite hydrogel: transferring the solution to a pressure kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 8-15h at the temperature of 100-150 ℃ to obtain reduced graphene oxide/crosslinked polyacrylamide/nickel salt composite hydrogel, and naturally cooling to room temperature;
(6) preparing reduced graphene oxide/crosslinked polyacrylamide/nickel salt composite aerogel: freezing the composite hydrogel for 0.5h at the low temperature of-196 ℃ by using liquid nitrogen, and drying the composite hydrogel for 8-24h in a freeze dryer to obtain the reduced graphene oxide/crosslinked polyacrylamide/nickel salt composite aerogel;
(7) sample calcination: putting the aerogel prepared in the step (6) into a porcelain boat, putting the porcelain boat into a quartz tube furnace, and adjusting the nitrogen flow to be 150cm3Min, aeration for 0.5h to remove air from the tube furnace, then nitrogen flow was adjusted to 50cm3Heating to 600-class 900 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 2h, closing the heat source, cooling the tube furnace to room temperature, closing the nitrogen source, heating to 250 ℃ at the heating rate of 5 ℃/min in the air atmosphere, keeping the temperature for 10h, and realizing the three-dimensional structure of graphene/nitrogen-doped carbon/nickel oxidePreparation of nanocomposite RGO/NPGC/Ni/NiO.
2. The method according to claim 1, wherein the polyacrylamide in the step (1) is any one of unhydrolyzed polyacrylamide and partially hydrolyzed polyacrylamide having a degree of hydrolysis of 5 to 25%.
3. The method according to claim 1, wherein the nickel salt in the step (2) is any one of nickel chloride and nickel nitrate.
4. The method according to claim 1, wherein the crosslinking agent in the step (3) is any one of phenol-formaldehyde and resorcinol-formaldehyde.
5. The method for preparing a graphene/nitrogen-doped carbon/nickel oxide composite material according to claim 1, wherein the graphene/nitrogen-doped carbon/nickel oxide nanocomposite material with a three-dimensional structure is prepared.
6. The method for preparing the graphene/nitrogen-doped carbon/nickel oxide composite material according to claim 5, wherein the three-dimensional graphene/nitrogen-doped carbon/nickel oxide nanocomposite material prepared by the method can be used for preparing electrodes of a supercapacitor.
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