CN109659142B - Graphite carbon/metal nitride composite nanotube array and preparation method and application thereof - Google Patents
Graphite carbon/metal nitride composite nanotube array and preparation method and application thereof Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
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- 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
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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
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Abstract
The invention relates to the field of electrode materials of super capacitors, in particular to a graphite carbon/metal nitride double-wall nanotube array and a preparation method thereof. The invention realizes the attachment of metal oxide on the surface of a graphite carbon layer and the double-layer coating of the graphite carbon and the metal nitride on the ZnO nano rod by a ZnO template electrodeposition method, and prepares the graphite carbon/metal nitride composite nanotube array by nitriding treatment and acid washing of the metal oxide. The preparation method can realize the controllable synthesis of the graphite carbon/metal nitride composite nanotube array, regulate and control the thickness of each layer of the graphite carbon layer and the metal nitride layer, obviously improve the conductivity of the metal nitride, improve the transmission speed of electroactive species and improve the performance of electrode materials. The method has simple process and is suitable for large-scale or industrial production, and the prepared graphite carbon/metal nitride composite nanotube array has excellent super-capacitance performance.
Description
Technical Field
The invention relates to the field of electrode materials of supercapacitors, in particular to a graphite carbon/metal nitride composite nanotube array and a preparation method and application thereof.
Background
The key component of a supercapacitor is the electrode material, the performance of which determines the performance of the supercapacitor. The nanotube array electrode is widely used for researching high-performance supercapacitor electrode materials due to the unique morphological advantages of high order, large specific surface area and the like. Transition metal oxide MnO2、NiO、Co3O4Hydroxide Co (OH)2、Ni(OH)2Lithium ion electrode material Li4Ti5O12、H2Ti6O13And the like, due to the advantages of low price, high capacitance performance and the like, the material has attracted wide attention of scientists as an electrode material of the super capacitor. However, a fatal disadvantage of the above materials is poor conductivity, which seriously affects the charge-discharge rate, energy density and power density of the electrode, and becomes a significant bottleneck in the development of capacitor electrode materials. Metal nitrides have received much attention due to their high electrical conductivity and are useful for improving the electrical conductivity of capacitor materials. However, at present, how to combine the metal nitride with the nanotube array to form a composite nanotube array, and to synergistically improve the conductivity of the material, has been a difficult point of research on conductive materials of the metal nitride nanotube array. At present, graphite carbon/metal nitride composite nanotube arrays with excellent electrochemical performance become research hotspots and difficulties in the field, and the formation of nanotubes by graphite carbon and metal nitride in a supercapacitor electrode material is still a big difficulty.
According to the invention, the transition metal nitride and the graphitic carbon are compounded to form the ordered composite nanotube array with high conductivity, so that the electron and ion transmission performance of the transition metal nitride can be obviously improved, and the abundant interface advantages and synergistic effects in the nanostructure are fully exerted, thereby obtaining the composite electrode material with low cost and high performance, and providing the electrode material with high conductivity for the production of the super capacitor.
Disclosure of Invention
The invention aims to solve the technical problem of providing a graphite carbon/metal nitride composite nanotube array in order to overcome the difficulty that graphite carbon and metal nitride in a super capacitor electrode material form a nanotube in the prior art.
The invention also aims to provide a preparation method of the graphite carbon/metal nitride composite nanotube array.
The invention also aims to provide the application of the graphite carbon/metal nitride composite nanotube array in the electrode material of the super capacitor.
In order to solve the technical problems, the invention adopts the technical scheme that:
a graphite carbon/metal nitride composite nanotube array is formed by compounding graphite carbon and metal nitride.
Compared with the accumulation of nano array electrode materials with other shapes, such as flaky materials, the tubular structure of the graphite carbon/metal nitride double-wall nanotube array can increase the specific surface area of the material, improve the capacitance of the electrode material, be beneficial to improving the charge-discharge speed of the electrode material and further improve the overall conductivity of the material.
By compounding the graphite carbon and the metal nitride, the conductivity of the metal nitride can be obviously improved, the transmission speed of electroactive species can be improved, the agglomeration of electrode materials can be well inhibited, and the performance of the electrode materials can be improved.
Preferably, the metal nitride is manganese nitride, cobalt nitride, iron nitride, nickel nitride or manganese cobalt nitride. Metal nitrides are generally more conductive than metal oxides and therefore are advantageous for achieving the fast electron transport properties required for capacitor materials. The conductivity of different metal nitrides has certain difference, and the conductivity of the whole capacitor material can be further improved by compounding the nitrides and the graphite carbon.
Preferably, the graphite carbon/metal nitride double-wall nanotube array has a tube diameter of 300-1000 nm, a length of 1-20 μm, a graphite carbon wall thickness of 20-200 nm, and a metal nitride wall thickness of 20-400 nm.
The composite nanotube consists of graphite carbon and metal nitride, the whole conductivity of the composite nanotube is mainly influenced by the thicknesses of two layers of materials, and the thickness of each wall layer directly influences the electron transmission path of an electrode material, so that the conductivity of the composite nanotube is influenced.
Preferably, the graphite carbon/metal nitride double-wall nanotube array has a tube diameter of 600-1000 nm, a length of 10-20 μm, a graphite carbon wall thickness of 50-150 nm, and a metal nitride wall thickness of 200-400 nm.
A preparation method of a graphite carbon/metal nitride composite nanotube array comprises the following steps:
s1, soaking a ZnO nanorod array into a pentose or hexose solution, and carrying out heat treatment under a vacuum condition to obtain a ZnO/graphite carbon composite nanorod array, wherein the concentration of the sugar solution is 1-10 mol/L, the soaking time is 0.5-6 h, the heat treatment temperature is 900-1100 ℃, and the heat treatment time is 1-6 h;
s2: taking the ZnO/graphitic carbon composite nanorod array prepared in S1 as a cathode, and preparing the ZnO/graphitic carbon/metal oxide composite nanorod array in a metal salt solution by an electrodeposition method, wherein the concentration of the metal salt solution is 0.5-2 mol/L, and the current density is 1-20 mA/cm2The electrodeposition time is 20-30 min;
s3: carrying out heat treatment on the ZnO/graphitic carbon/metal oxide composite nanorod array prepared in the step S2 under ammonia gas to obtain a ZnO/graphitic carbon/metal nitride composite nanorod array, wherein the heat treatment temperature is 500-1000 ℃, the heat treatment time is 0.5-2 h, and the ammonia gas flow is 20-200 sccm;
s4: and (3) carrying out acid treatment on the ZnO/graphite carbon/metal nitride composite nanorod array prepared in the step (S3) to obtain a graphite carbon/metal nitride composite nanotube array, wherein the acid concentration is 0.2-1.0 mol/L, and the acid treatment time is 0.2-2 h.
Generally, the nitride is synthesized by directly nitriding densely distributed metal oxide particles under the condition of ammonia gas, and the heat treatment condition is easy to cause melting and aggregation of the generated nitride particles.
In order to overcome the difficulty of forming the composite nanotube array by the graphite carbon and the metal nitride in the prior art, the inventor finds that the preparation of the graphite carbon/metal nitride composite nanotube array can be well realized by the electrodeposition method guided by the ZnO template method through continuous experiments. The metal oxide can be well attached to the surface of the graphite carbon layer through electrochemical deposition, the double-layer coating of the ZnO nano-rod by the graphite carbon and the metal nitride is realized, the graphite carbon/metal nitride composite nano-tube array is prepared through the nitridation treatment and the acid washing of the metal oxide, and the thickness of the tube wall of the graphite carbon and the metal nitride can be well controlled through the electrodeposition. In the heat treatment process, the vacuum condition can ensure that the graphite carbon nano tube is not oxidized, and the electric conductivity of the graphite carbon nano tube is better ensured.
Preferably, the sugar solution concentration in S1 is 2-6 mol/L, the immersion time is 0.5-1 h, the heat treatment temperature is 1000 ℃, and the heat treatment time is 1-3 h.
Preferably, the heat treatment time in S1 is 3 hours. The heat treatment time directly affects the thickness of the graphite layer and the degree of graphitization.
Preferably, the metal salt solution in S2 is Mn (NO)3)2、Fe(NO3)2、Co(NO3)2Or Ni (NO)3)2。
More preferably, the metal salt solution in the above S2 is Co (NO)3)2. The composite array of Co oxide and graphite carbon has excellent electrochemical performance and stability.
Preferably, the acid treatment time in S4 is 20 min. And in the acid treatment step, the nanotube array collapses due to too high acid concentration, a tubular material cannot be obtained, the ZnO nanorod cannot be removed due to too low acid concentration, the nanotube array cannot be obtained, and the graphite carbon/metal nitride composite nanotube array can be synthesized controllably by controlling the acid concentration of the acid treatment.
Preferably, the acid treated in S4 is hydrochloric acid or sulfuric acid or acetic acid.
More preferably, the acid is acetic acid. The acidity is low, and the corrosion process of the zinc oxide can be well controlled.
The ZnO nanorod array can be an existing ZnO nanorod array, and can also be prepared by the following method: in Zn (NO)3)2Adding ammonium acetate into the aqueous solution, keeping the temperature constant, stirring, and carrying out electrodeposition to obtain a ZnO nanorod array, wherein the constant temperature is 60-100 ℃, the constant temperature time is 0.5-6 hours, and the stirring time is 2-30 min.
Preferably, the Zn (NO)3)2The concentration of the aqueous solution is 0.01-4.00 mol/L, and the concentration of ammonium acetate is 0.01-0.1 mol/Ll/L。
Preferably, the cathode of the electrodeposition is a metallic titanium sheet, the electrodeposition time is 1-3 h, and the current density is 1-10 mA/cm2。
Preferably, the electrodeposition time is 2 h. Through electrochemical deposition, the synthesis of the ZnO nanorod array can be well realized, and the thickness of the ZnO nanorod array can be well controlled by controlling the battery time, so that the pipe diameter of the graphitic carbon/metal nitride double-wall nanotube array is controlled.
The graphite carbon/metal nitride composite nanotube array can be used as an electrode material to be applied to a super capacitor. The graphite carbon/metal nitride composite nanotube array has excellent charge and discharge speed and energy density, fully combines the excellent electrical properties of graphite carbon and metal nitride, compounds the transition metal nitride and the graphite carbon to form the ordered composite nanotube array with high conductivity, can obviously improve the electron and ion transmission properties of the transition metal nitride, and fully exerts the rich interface advantages and synergistic effect in the nanostructure, thereby obtaining a low-cost and high-performance composite electrode material and providing a high-conductivity electrode material for the production of a super capacitor.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a graphite carbon/metal nitride composite nanotube array, which is a high-conductivity ordered composite double-wall nanotube array formed by compounding metal nitride and graphite carbon, wherein the tubular structure of the double-wall nanotube array can increase the specific surface area of a material, improve the capacitance of an electrode material, facilitate the improvement of the charge-discharge speed of the electrode material, and has excellent charge-discharge speed and energy density.
Drawings
FIG. 1 is a flow chart of a method for preparing a graphitic carbon/metal nitride composite nanotube array.
Fig. 2 is a scanning electron micrograph (2000 times magnification) of the graphitic carbon/metal nitride composite nanotube array prepared in example 1.
Fig. 3 is a cyclic voltammogram of the graphite carbon/metal nitride composite nanotube array prepared in example 1 at different scanning speeds.
Fig. 4 is a charge (a) discharge (b) electrical curve diagram of the graphitic carbon/metal nitride composite nanotube array prepared in example 1 under different constant currents.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
A graphite carbon/metal nitride composite nanotube array is formed by compounding graphite carbon and metal nitride cobalt nitride, wherein the pipe diameter of the graphite carbon/metal nitride double-walled nanotube array is 600nm, the length of the graphite carbon/metal nitride double-walled nanotube array is 10 mu m, the thickness of the graphite carbon wall is 50nm, and the thickness of the cobalt nitride wall is 250 nm.
The graphite carbon/metal nitride composite nanotube array is prepared by an electrodeposition method guided by a ZnO template method according to the following steps:
s1: soaking the ZnO nanorod array into 3mol/L glucose solution for 60 minutes, and then carrying out heat treatment for 3 hours at 1000 ℃ under a vacuum condition to obtain a ZnO/graphite carbon composite nanorod array;
s2: taking a ZnO/graphite carbon composite nanorod array as a cathode, and adding 1.0mol/L Co (NO)3)2In solution, at a current density of 3.0mA/cm2Performing electrodeposition for 30 minutes to obtain a ZnO/graphitic carbon/metal oxide composite nanorod array;
s3: carrying out ammonia heat treatment on the ZnO/graphitic carbon/metal oxide composite nanorod array at 800 ℃ for 2 hours, wherein the flow of ammonia is 100sccm, so as to obtain a ZnO/graphitic carbon/metal nitride composite nanorod array;
s4: and (3) treating the ZnO/graphitic carbon/metal nitride composite nanorod array in a solution with the concentration of acetic acid of 0.5mol/L for 1 hour to obtain the graphitic carbon/metal nitride composite nanotube array.
The preparation method of the ZnO nanorod array comprises the following steps: 148.75 g of Zn (NO) are taken3)2Salt, which is dissolved in water to form a 500 ml solution (1.0mol/L), and 0.35 g ammonium acetate (0.01mol/L) is added thereto, and the mixture is kept at a constant temperature of 60 ℃ for 1 hour, stirred for 10 minutes by using 1cm2A titanium sheet is taken as a cathode, and is electrodeposited in the solution for 30 minutes, and the current density is 5mA/cm2And preparing the ZnO nanorod array.
FIG. 1 is a flow chart of the preparation of a graphitic carbon/metal nitride composite nanotube array.
The scanning electron microscope image of the prepared graphitic carbon/metal nitride composite nanotube array is shown in fig. 2, and the nanotube array with ordered arrangement can be obviously seen from fig. 2.
The cyclic voltammogram of the graphitic carbon/metal nitride composite nanotube array is shown in fig. 3, which shows that the material has good super-capacitance performance. FIG. 3 is a cyclic voltammetry curve with a scanning speed of 100mV/s, a potential window of-0.8-0V, and the curve is an approximate rectangle with good symmetry, which shows that the material has good double-layer capacitance characteristics, and the specific capacitance calculated is 72mF/cm2。
The charge-discharge curve diagram of the graphitic carbon/metal nitride composite nanotube array is shown in fig. 4, which shows that the material has good charge-discharge performance. FIG. 4 is a graph showing a current density of 6mA/cm2The charge/discharge curve of (2) shows good symmetry and also shows good electric double layer capacitance characteristics. The specific capacitance is calculated to be 70mF/cm2。
Example 2
A graphite carbon/metal nitride composite nanotube array is formed by compounding graphite carbon and metal nitride cobalt nitride, wherein the pipe diameter of the graphite carbon/metal nitride double-walled nanotube array is 600nm, the length of the graphite carbon/metal nitride double-walled nanotube array is 10 mu m, the thickness of the graphite carbon wall is 60nm, and the thickness of the cobalt nitride wall is 120 nm.
Example 3
A graphite carbon/metal nitride composite nanotube array is formed by compounding graphite carbon and metal nitride cobalt nitride, wherein the pipe diameter of the graphite carbon/metal nitride double-walled nanotube array is 1000nm, the length of the graphite carbon/metal nitride double-walled nanotube array is 10 mu m, the thickness of the graphite carbon wall is 150nm, and the thickness of the cobalt nitride wall is 200 nm.
Example 4
A graphite carbon/metal nitride composite nanotube array is formed by compounding graphite carbon and metal nitride cobalt nitride, wherein the pipe diameter of the graphite carbon/metal nitride double-walled nanotube array is 600nm, the length of the graphite carbon/metal nitride double-walled nanotube array is 1 mu m, the thickness of the graphite carbon wall is 150nm, and the thickness of the cobalt nitride wall is 200 nm.
Example 5
A graphite carbon/metal nitride composite nanotube array is formed by compounding graphite carbon and metal nitride cobalt nitride, wherein the pipe diameter of the graphite carbon/metal nitride double-walled nanotube array is 600nm, the length of the graphite carbon/metal nitride double-walled nanotube array is 20 mu m, the thickness of the graphite carbon wall is 150nm, and the thickness of the cobalt nitride wall is 200 nm.
Example 6
A graphite carbon/metal nitride composite nanotube array is formed by compounding graphite carbon and metal nitride cobalt nitride, wherein the pipe diameter of the graphite carbon/metal nitride double-walled nanotube array is 600nm, the length of the graphite carbon/metal nitride double-walled nanotube array is 10 mu m, the thickness of the graphite carbon wall is 20nm, and the thickness of the cobalt nitride wall is 200 nm.
Example 7
A graphite carbon/metal nitride composite nanotube array is formed by compounding graphite carbon and metal nitride cobalt nitride, wherein the pipe diameter of the graphite carbon/metal nitride double-walled nanotube array is 600nm, the length of the graphite carbon/metal nitride double-walled nanotube array is 10 mu m, the thickness of the graphite carbon wall is 200nm, and the thickness of the cobalt nitride wall is 200 nm.
Example 8
A graphite carbon/metal nitride composite nanotube array is formed by compounding graphite carbon and metal nitride cobalt nitride, wherein the pipe diameter of the graphite carbon/metal nitride double-walled nanotube array is 600nm, the length of the graphite carbon/metal nitride double-walled nanotube array is 10 mu m, the thickness of the graphite carbon wall is 150nm, and the thickness of the cobalt nitride wall is 400 nm.
Example 9
A graphite carbon/metal nitride composite nanotube array is formed by compounding graphite carbon and metal nitride cobalt nitride, wherein the pipe diameter of the graphite carbon/metal nitride double-walled nanotube array is 600nm, the length of the graphite carbon/metal nitride double-walled nanotube array is 10 mu m, the thickness of the graphite carbon wall is 100nm, and the thickness of the cobalt nitride wall is 20 nm.
Example 10
A preparation method of a graphite carbon/metal nitride composite nanotube array comprises the following steps:
s1: soaking the ZnO nanorod array into 3mol/L glucose solution for 30 minutes, and then carrying out heat treatment for 1 hour at 1000 ℃ under a vacuum condition to obtain a ZnO/graphite carbon composite nanorod array;
s2: ZnO/graphite carbon composite nanorod array is used as a cathode, and the concentration of Co (NO) is 2mol/L3)2In solution, at a current density of 20.0mA/cm2Performing electrodeposition for 20 minutes to obtain a ZnO/graphite carbon/metal oxide composite nanorod array, wherein the flow of ammonia gas is 200 sccm;
s3: carrying out ammonia heat treatment on the ZnO/graphitic carbon/metal oxide composite nanorod array at 800 ℃ for 30 minutes at the ammonia flow of 200sccm to prepare the ZnO/graphitic carbon/metal nitride composite nanorod array;
s4: and (3) treating the ZnO/graphitic carbon/metal nitride composite nanorod array in a solution with the concentration of acetic acid of 0.2mol/L for 2 hours to obtain the graphitic carbon/metal nitride composite nanotube array.
The preparation method of the ZnO nanorod array comprises the following steps: 29.74 g of Zn (NO) are taken3)2Salt, dissolving in water to form 500 ml solution (0.2mol/L), adding 0.14 g ammonium acetate (0.02mol/L), keeping at 60 deg.C for 30min, stirring for 5 min, and using 1cm2A titanium metal sheet is taken as a cathode and is electrodeposited in the solution for 12 minutes at a current density of10mA/cm2And obtaining the ZnO nanorod array.
The graphite carbon/metal nitride composite nanotube array is prepared by an electrodeposition method guided by a ZnO template method according to the following steps.
Example 11
A preparation method of a graphite carbon/metal nitride composite nanotube array comprises the following steps:
s1: soaking the ZnO nanorod array into 2mol/L glucose solution for 40 minutes, and then carrying out heat treatment for 2 hours at 1000 ℃ under a vacuum condition to obtain a ZnO/graphite carbon composite nanorod array;
s2: taking a ZnO/graphite carbon composite nanorod array as a cathode, and adding 0.5mol/L Co (NO)3)2In solution, at a current density of 10.0mA/cm2Carrying out electrodeposition for 30min to obtain a ZnO/graphitic carbon/metal oxide composite nanorod array;
s3: carrying out ammonia heat treatment on the ZnO/graphitic carbon/metal oxide composite nanorod array at 800 ℃ for 1 hour, wherein the flow of ammonia is 100sccm, so as to obtain a ZnO/graphitic carbon/metal nitride composite nanorod array;
s4: and (3) treating the ZnO/graphitic carbon/metal nitride composite nanorod array in a solution with the concentration of acetic acid of 0.3mol/L for 50 minutes to obtain the graphitic carbon/metal nitride composite nanotube array.
The preparation method of the ZnO nanorod array comprises the following steps: 72.37 g of Zn (NO) are taken3)2Dissolving salt in water to obtain 500 ml solution (0.5mol/L), adding 0.7 g ammonium acetate (0.1mol/L), keeping constant temperature at 60 deg.C for 40min, stirring for 7 min, and collecting the filtrate with a volume of 1cm2A titanium sheet is taken as a cathode, and is electrodeposited in the solution for 15 minutes, and the current density is 8mA/cm2And obtaining the ZnO nanorod array.
Example 12
A preparation method of a graphite carbon/metal nitride composite nanotube array comprises the following steps:
s1: soaking the ZnO nanorod array into a 4mol/L glucose solution for 30 minutes, and then carrying out heat treatment for 2.5 hours at 1000 ℃ under a vacuum condition to obtain a ZnO/graphitic carbon composite nanorod array;
s2: taking ZnO/graphite carbon composite nanorod array as a cathode, and adding 0.75mol/L Co (NO)3)2In solution, at a current density of 4.0mA/cm2Performing electrodeposition for 20min to obtain a ZnO/graphitic carbon/metal oxide composite nanorod array;
s3, performing ammonia heat treatment on the ZnO/graphitic carbon/metal oxide composite nanorod array at 800 ℃ for 90 minutes, wherein the flow of ammonia is 50sccm, so as to obtain the ZnO/graphitic carbon/metal nitride composite nanorod array;
and S4, treating the ZnO/graphite carbon/metal nitride composite nanorod array in a solution with the concentration of acetic acid being 0.75mol/L for 20 minutes to obtain the graphite carbon/metal nitride composite nanotube array.
The preparation method of the ZnO nanorod array comprises the following steps: 111.56 g of Zn (NO) are taken3)2Dissolving salt in water to obtain 500 ml solution (0.75mol/L), adding 2.1 g ammonium acetate (0.3mol/L), keeping constant temperature at 60 deg.C for 1 hr, stirring for 10 min, and collecting the filtrate with a volume of 1cm2A titanium sheet is taken as a cathode, and is electrodeposited in the solution for 20 minutes, and the current density is 6mA/cm2And preparing the ZnO nanorod array.
Example 13
A preparation method of a graphite carbon/metal nitride composite nanotube array comprises the following steps:
s1: soaking the ZnO nanorod array into 5mol/L glucose solution for 30min, and then carrying out heat treatment for 2 hours at 1000 ℃ under a vacuum condition to obtain a ZnO/graphite carbon composite nanorod array;
s2, taking the ZnO/graphite carbon composite nanorod array as a cathode at the concentration of 1.0mol/LNi (NO)3)2In solution, at a current density of 2.0mA/cm2Performing electrodeposition for 30min to obtain a ZnO/graphitic carbon/metal oxide composite nanorod array;
s3: carrying out ammonia gas heat treatment on the ZnO/graphitic carbon/metal oxide composite nanorod array at the temperature of 900 ℃ for 1.5 hours, wherein the flow of ammonia gas is 20sccm, so as to obtain the ZnO/graphitic carbon/metal nitride composite nanorod array;
s4: and (3) treating the ZnO/graphitic carbon/metal nitride composite nanorod array in a solution with the acetic acid concentration of 1.0mol/L for 20 minutes to obtain the graphitic carbon/metal nitride composite nanotube array.
The preparation method of the ZnO nanorod array comprises the following steps: 297.5 g of Zn (NO) are taken3)2Salt, which is dissolved in water to form a 500 ml solution (2mol/L), and 15.4 g ammonium acetate (0.4mol/L) is added, and the mixture is kept at 70 ℃ for 30 minutes, stirred for 15 minutes, and utilized by 1cm2A titanium sheet is taken as a cathode, and is electrodeposited in the solution for 30 minutes, and the current density is 4mA/cm2And preparing the ZnO nanorod array.
Example 14
A preparation method of a graphite carbon/metal nitride composite nanotube array comprises the following steps:
s1: soaking the ZnO nanorod array into 6mol/L glucose solution for 30min, and then carrying out heat treatment for 6 hours at 1000 ℃ under a vacuum condition to obtain a ZnO/graphite carbon composite nanorod array;
s2: ZnO/graphite carbon composite nano rod array is used as a cathode and the concentration is 1.0mol/LMn (NO)3)2In solution, at a current density of 3.0mA/cm2Performing electrodeposition for 20min to obtain a ZnO/graphitic carbon/metal oxide composite nanorod array;
s3: carrying out ammonia heat treatment on the ZnO/graphitic carbon/metal oxide composite nanorod array at 1000 ℃ for 1 hour, wherein the flow of ammonia is 20sccm, so as to obtain a ZnO/graphitic carbon/metal nitride composite nanorod array;
s4: and (3) treating the ZnO/graphitic carbon/metal nitride composite nanorod array in a solution with the acetic acid concentration of 0.25mol/L for 2 hours to prepare the graphitic carbon/metal nitride composite nanotube array.
The preparation method of the ZnO nanorod array comprises the following steps: 595 g of Zn (NO) are taken3)2Salt, which is dissolved in water to form a 500 ml solution (4mol/L), and 30.8 g ammonium acetate (0.8mol/L) is added, and the mixture is kept at 80 ℃ for 30 minutes and stirred for 2 minutes by using 1.5cm2A titanium sheet is taken as a cathode, and is electrodeposited in the solution for 60 minutes, and the current density is 2mA/cm2Preparation ofAnd (4) obtaining the ZnO nanorod array.
Result detection
The dimensions of the graphitic carbon/metal nitride composite nanotube arrays prepared in examples 10-14 are shown in table 1 below.
TABLE 1
| Serial number | Pipe diameter/nm | Length/mum | Graphite carbon wall thickness/nm | Thickness/nm of metal nitride wall |
| Example 10 | 800 | 10 | 25 | 400 |
| Example 11 | 600 | 10 | 25 | 330 |
| Example 12 | 600 | 10 | 40 | 180 |
| Example 13 | 400 | 10 | 45 | 180 |
| Example 14 | 400 | 10 | 40 | 200 |
The electrochemical performance of the graphite carbon/metal nitride composite nanotube array prepared by the invention is detected, and the detection indexes are as follows: the capacitance, the charge and discharge rate and the energy density were measured, and the results are shown in Table 2.
The specific capacitance detection method comprises the following steps: and (4) obtaining a cyclic voltammetry curve of the device at a sweep rate of 100mV/s, and calculating to obtain the specific capacitance.
The detection (or calculation) method of the energy density comprises the following steps:
wherein E represents energy density of W.h/Kg or mW.h/cm3；
CspThe specific capacitance value is F/g obtained by testing a two-electrode system;
u is the potential window difference in the electrochemical test;
p is power density, W/Kg or mW/cm3；
t represents the discharge time, s.
TABLE 2
Claims (9)
1. A graphite carbon/metal nitride composite nanotube array is characterized in that a graphite carbon/metal nitride double-walled nanotube array is formed by compounding graphite carbon and metal nitride; the preparation method of the graphite carbon/metal nitride composite nanotube array comprises the following steps:
s1, soaking a ZnO nanorod array into a pentose or hexose solution, and carrying out heat treatment under a vacuum condition to obtain a ZnO/graphite carbon composite nanorod array, wherein the concentration of the sugar solution is 1-10 mol/L, the soaking time is 0.5-6 h, the heat treatment temperature is 900-1100 ℃, and the heat treatment time is 1-6 h;
s2: taking the ZnO/graphitic carbon composite nanorod array prepared in S1 as a cathode, and preparing the ZnO/graphitic carbon/metal oxide composite nanorod array in a metal salt solution by an electrodeposition method, wherein the concentration of the metal salt solution is 0.5-2 mol/L, and the current density is 1-20 mA/cm2The electrodeposition time is 20-30 min;
s3: carrying out heat treatment on the ZnO/graphitic carbon/metal oxide composite nanorod array prepared in the step S2 under ammonia gas to obtain a ZnO/graphitic carbon/metal nitride composite nanorod array, wherein the heat treatment temperature is 500-1000 ℃, the heat treatment time is 0.5-2 h, and the ammonia gas flow is 20-200 sccm;
s4: and (3) carrying out acid treatment on the ZnO/graphite carbon/metal nitride composite nanorod array prepared in the step (S3) to obtain a graphite carbon/metal nitride composite nanotube array, wherein the acid concentration is 0.2-1.0 mol/L, and the acid treatment time is 0.2-2 h.
2. The graphitic carbon/metal nitride composite nanotube array according to claim 1, wherein the metal nitride is manganese nitride, cobalt nitride, iron nitride, nickel nitride or manganese cobalt nitride.
3. The graphitic carbon/metal nitride composite nanotube array according to claim 1, wherein the graphitic carbon/metal nitride double-walled nanotube array has a tube diameter of 300-1000 nm, a length of 1-20 μm, a graphitic carbon wall thickness of 20-200 nm, and a metal nitride wall thickness of 20-400 nm.
4. The graphitic carbon/metal nitride composite nanotube array according to claim 1, wherein the metal salt solution in S2 is Mn (NO)3)2、Fe(NO3)2、Co(NO3)2Or Ni (NO)3)2。
5. The graphitic carbon/metal nitride composite nanotube array according to claim 1, wherein the acid treatment time in S4 is 20 min.
6. The graphitic carbon/metal nitride composite nanotube array according to claim 1, wherein the ZnO nanorod array in S1 is prepared by the following steps: in Zn (NO)3)2Adding ammonium acetate into the aqueous solution, keeping the temperature constant, stirring, and carrying out electrodeposition to obtain a ZnO nanorod array, wherein the constant temperature is 60-100 ℃, the constant temperature time is 0.5-6 hours, and the stirring time is 2-30 min.
7. The graphitic carbon/metal nitride composite nanotube array according to claim 6, wherein said Zn (NO) is3)2The concentration of the aqueous solution is 0.2-4.00 mol/L, and the concentration of ammonium acetate is 0.01-0.8 mol/L.
8. The graphitic carbon/metal nitride composite nanotube array according to claim 6, wherein the cathode of the electrodeposition in the ZnO nanorod array prepared by electrodeposition is a metallic titanium sheet, the electrodeposition time is 12-60 min, and the current density is 1-10 mA/cm2。
9. The application of the graphitic carbon/metal nitride composite nanotube array according to any one of claims 1 to 8 in supercapacitor electrode materials.
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