CN113381015B - Nitrogen-doped hollow amorphous carbon shell material, preparation method and application - Google Patents
Nitrogen-doped hollow amorphous carbon shell material, preparation method and application Download PDFInfo
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Abstract
The invention provides a nitrogen-doped hollow amorphous carbon shell material, a preparation method and application thereof. The nitrogen-doped hollow amorphous carbon shell cathode material is of a rod-shaped hollow structure, and the unique hollow structure and the sodium affinity of nitrogen can effectively reduce nucleation overpotential and improve cycle performance.
Description
Technical Field
The invention relates to the field of new energy electrochemistry, in particular to a nitrogen-doped hollow amorphous carbon shell material, a preparation method and application.
Background
With the limitation of conventional energy and the increasing environmental problems, secondary batteries conforming to green sustainable development have drawn much attention. Compared with lithium ion batteries, sodium ion batteries have acceptable energy density, abundant sodium resources which are 1000 times of that of lithium, and low manufacturing cost of sodium. Thus, people look away from lithium ion batteries to sodium ion batteries. In sodium ion batteries, sodium metal has a high theoretical capacity of 1166 mAh g -1 And a standard hydrogen electrode with low electrochemical potential-2.714V vs. is a research hotspot in the negative electrode material of the sodium-ion battery. However, sodium metal has high reactivity and infinite volume change, and forms an unstable Solid Electrolyte Interface (SEI) film when the sodium metal reacts with an electrolyte solution, resulting in poor cycle and rate properties, and low coulombic efficiency. Dendrites caused by uneven deposition of sodium ions during deposition can also puncture the membrane, causing safety issues. The dead sodium produced by the stripping from the bottom or middle of the dendrite during the stripping process increases the voltage polarization and the overall resistance of the cell.
Disclosure of Invention
The invention provides a nitrogen-doped hollow amorphous carbon shell material, a preparation method and application, and solves the problems that a dendritic crystal pierces a diaphragm due to uneven sodium ion deposition and dead sodium can increase voltage polarization and total resistance of a battery at present.
The technical scheme for realizing the invention is as follows:
a method for preparing a nitrogen-doped hollow amorphous carbon shell sodium metal battery cathode material comprises the steps of firstly preparing a zinc oxide nanorod solution by a water bath method, and centrifugally drying to obtain white zinc oxide powder. And then slowly dripping a Tris buffer into a dopamine hydrochloride solution, pouring a zinc oxide nano rod into a dopamine hydrochloride and Tris mixed solution, stirring for 12 hours in a dark environment, centrifugally drying, annealing in an argon atmosphere to obtain a nitrogen-doped carbon shell coated zinc oxide material, and finally etching the zinc oxide with hydrochloric acid to obtain the nitrogen-doped hollow carbon shell. The unique hollow structure and the sodium affinity of nitrogen can effectively reduce the nucleation overpotential and improve the cycle performance.
A preparation method of a nitrogen-doped hollow amorphous carbon shell sodium metal battery cathode material comprises the following steps:
(1) preparing zinc oxide nanorod powder;
(2) respectively dissolving Tris and dopamine hydrochloride in alcohol and deionized water, and then slowly dropwise adding a Tris buffer solution into the dopamine hydrochloride solution;
(3) adding zinc oxide powder into a Tris buffer solution and a dopamine hydrochloride solution, and stirring for 12 hours in a dark environment;
(4) centrifugally drying the solution obtained in the step (3), and annealing for 4-6 hours at the temperature of 600-800 ℃ in the argon atmosphere to obtain nitrogen-doped amorphous carbon shell coated zinc oxide powder;
(5) and (5) etching the black powder obtained in the step (4) in a prepared hydrochloric acid solution for 2 hours to obtain the nitrogen-doped hollow amorphous carbon shell. The material is used for the cathode material of the sodium metal battery.
The preparation process of the zinc oxide nanorod powder in the step (1) is as follows: dissolving zinc acetate dihydrate and hexamethylenetetramine in deionized water, heating in a water bath for reaction, and centrifugally drying the obtained white solution to obtain white zinc oxide powder.
The mass ratio of the zinc acetate dihydrate to the hexamethylenetetramine to the deionized water is 1.1: 0.7: 200, heating in water bath at 90 deg.c for 5 hr.
The solvent in the step (2) is a mixed solvent of alcohol and deionized water; the mass ratio of the dopamine hydrochloride, the alcohol and the deionized water is (110- & lt 120- & gt): 37: 17; the mass ratio of Tris buffer to alcohol to deionized water is (40-45): 2: 1, the volume ratio of the dopamine hydrochloride solution to the Tris buffer solution is (27-30): 3.
the mass ratio of the mixed solution to the zinc oxide nanorod powder in the step (3) is 100: (0.1-1).
In the step (5), the concentration of hydrochloric acid is 3-5 mol/L, and the etching time is 2-3 hours.
The nitrogen-doped hollow amorphous carbon shell material is a rod-shaped hollow structure with the length of 3-4 mu m and the diameter of 400 nm.
The invention has the beneficial effects that:
(1) the amorphous carbon shell has high Young modulus (approximately equal to 0.64 Tpa), high elastic modulus (1.28 +/-0.50 Tpa) and large specific surface area (292.58 m) 2 g -1 ) High conductivity (≈ 3000W m) -1 K -1 ) And the like.
(2) The space inside the hollow amorphous carbon shell can accommodate the change in volume of sodium metal.
(3) The nitrogen element doping can easily form a sodium-philic surface, thereby ensuring that the flux of sodium ions is uniform, effectively reducing the nucleation overpotential and improving the cycle performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is scanning electron microscope and transmission electron microscope images of the zinc oxide nanorods (a, b) and the nitrogen-doped hollow amorphous carbon shells (c, d) prepared in example 1 at different magnifications.
Fig. 2 is an XPS spectrum of a nitrogen-doped hollow amorphous carbon shell prepared in example 1.
FIG. 3 is a graph of the nitrogen-doped hollow amorphous carbon shell electrode at 0.5 mA cm in example 1 -2 、1 mAh cm -2 Voltage capacity curve of.
FIG. 4 shows the nitrogen-doped hollow amorphous carbon shell electrode at 1 mA cm in example 1 -2 、1 mAh cm -2 Coulomb efficiency plot of the lower.
FIG. 5 shows the nitrogen-doped hollow amorphous carbon shell electrode of example 1 at 2 mA cm -2 、2 mAh cm -2 Cycle performance graph below.
FIG. 6 shows a total cell of example 1 with a vanadium sodium phosphate coated carbon layer as the positive electrode and a Na @ nitrogen doped hollow amorphous carbon shell as the negative electrode at 100 mA g -1 Current density of (a).
Detailed Description
The technical solutions of the present invention will be described clearly and completely below with reference to embodiments of the present invention, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art based on the embodiments of the present invention without inventive step, are within the scope of the present invention.
Example 1
A preparation method of a nitrogen-doped hollow amorphous carbon shell sodium metal battery negative electrode material comprises the following steps:
(1) zinc oxide nano rod
The zinc oxide nano rod is synthesized by a water bath method.
The preparation steps are as follows: adding zinc acetate dihydrate (C) 4 H 6 O 4 ·Zn·2H 2 O, 1.1 g), hexamethylenetetramine (C) 6 H 12 N 4 0.7 g) of zinc oxide powder is dissolved in 200 ml of deionized water, heated for 5 hours in a water bath at the temperature of 90 ℃, and centrifugally dried to obtain white zinc oxide powder.
(2) Preparation of nitrogen-doped hollow amorphous carbon shell
240 mg of dopamine hydrochloride is dissolved in 74 ml of alcohol and 34 ml of deionized water, 180 mg of Tris is dissolved in 8 ml of alcohol and 4 ml of deionized water, and then Tris buffer is slowly added dropwise to the dopamine hydrochloride solution.
Pouring the zinc oxide powder in the step (1) into the solution, and stirring for 12 hours in the dark. And then centrifugally drying, and annealing for 6 hours at 600 ℃ in an argon atmosphere to obtain the zinc oxide coated by the nitrogen-doped amorphous carbon shell.
Preparing a 5 mol/L hydrochloric acid solution, pouring the annealed zinc oxide powder coated by the nitrogen-doped amorphous carbon shell into the prepared hydrochloric acid solution, etching for 2 hours, and centrifugally drying to obtain the nitrogen-doped hollow carbon shell.
Assembling and testing electrochemical performance of the button cell:
electrochemical performance testing was performed by CR2032 button cell at room temperature. The working electrode is prepared as follows: firstly, a sample material, acetylene black and carboxymethyl cellulose (CMC) are mixed according to the weight ratio of 8:1:1, and are ground for 20 minutes, then a proper amount of deionized water is dripped into the mixed sample, and the mixture is ground for 10 minutes to form uniform slurry. Secondly, uniformly scraping the obtained slurry on a copper foil by using a scraper, then drying for 4 hours at 80 ℃ in a vacuum drying oven, and then drying for 12 hours at 120 ℃ in vacuum, and removing the solvent; finally, the copper foil coated with the sample was pressed into small wafers with a dicing machine.
In the embodiment, the half-cell adopts a nitrogen-doped amorphous carbon shell as a positive electrode, a sodium sheet as a negative electrode, Celgard 2400 as a diaphragm, and an electrolyte is 1M NaPF dissolved in ethylene carbonate and diethyl carbonate (in a volume ratio of 1: 1) 6 The charge and discharge test is completed under a Xinwei battery test system, the upper limit of the test voltage range is 0.1V, the test temperature is room temperature, and the nitrogen-doped hollow amorphous carbon shell material is 0.5 mA cm -2 The nucleation overpotential was 5.6 mV at current density of (1). At a current density of 1 mA cm -2 The capacity is 1 mAh cm -2 In the case of (2), the cycle can be stabilized for 800 hours or more, and the coulomb efficiency value is 98.And 53 percent. At a current density of 2 mA cm -2 The capacity is 2 mAh cm -2 In the case of (3), the cycle was also stabilized for 800 hours.
Respectively taking a vanadium sodium phosphate coated carbon layer and a Na @ nitrogen doped hollow amorphous carbon shell as a positive electrode and a negative electrode to assemble a full cell, and 100 mA g -1 After the circulation is performed for 100 times, the capacity is 81.46 mAh g -1 . These data demonstrate that the prepared nitrogen-doped hollow carbon shell has lower nucleation overpotential and better cycling stability, and also has higher capacity in full cells.
Example 2
A preparation method of a nitrogen-doped hollow amorphous carbon shell sodium metal battery negative electrode material comprises the following steps:
(1) zinc oxide nano rod
The zinc oxide nano rod is synthesized by a water bath method.
The preparation steps are as follows: adding zinc acetate dihydrate (C) 4 H 6 O 4 ·Zn·2H 2 O, 1.1 g), hexamethylenetetramine (C) 6 H 12 N 4 0.7 g) of zinc oxide powder is dissolved in 200 mL of deionized water, heated for 5 hours at the temperature of 90 ℃ in a water bath, and centrifugally dried to obtain white zinc oxide powder.
(2) Preparation of nitrogen-doped hollow amorphous carbon shell
230 mg dopamine hydrochloride was dissolved in 74 ml alcohol and 34 ml deionized water, 170 mg Tris was dissolved in 8 ml alcohol and 4 ml deionized water, after which Tris buffer was slowly added dropwise to the dopamine hydrochloride solution. Pouring the zinc oxide powder in the step (1) into the solution, and stirring for 12 hours in the dark. And then centrifugally drying, and annealing for 6 hours at 600 ℃ in an argon atmosphere to obtain the zinc oxide coated by the nitrogen-doped amorphous carbon shell.
Preparing a 5 mol/L hydrochloric acid solution, pouring the annealed zinc oxide powder coated by the nitrogen-doped amorphous carbon shell into the prepared hydrochloric acid solution, etching for 2 hours, and centrifugally drying to obtain the nitrogen-doped hollow carbon shell.
Example 3
The preparation method of the nitrogen-doped hollow amorphous carbon shell sodium metal battery cathode material comprises the following steps:
(1) zinc oxide nano rod
The zinc oxide nano rod is synthesized by a water bath method.
The preparation steps are as follows: adding zinc acetate dihydrate (C) 4 H 6 O 4 ·Zn·2H 2 O, 1.1 g), hexamethylenetetramine (C) 6 H 12 N 4 0.7 g) of zinc oxide is dissolved in 200 mL of deionized water, heated in a water bath at 90 ℃ for 5 hours, and centrifugally dried to obtain white zinc oxide powder.
(2) Preparation of nitrogen-doped hollow amorphous carbon shell
230 mg dopamine hydrochloride was dissolved in 74 ml alcohol and 34 ml deionized water, 160 mg Tris was dissolved in 8 ml alcohol and 4 ml deionized water, after which Tris buffer was slowly added dropwise to the dopamine hydrochloride solution. Pouring the zinc oxide powder in the step (1) into the solution, and stirring for 12 hours in the dark. And then centrifugally drying, and annealing for 4 hours at 700 ℃ in an argon atmosphere to obtain the zinc oxide coated by the nitrogen-doped amorphous carbon shell.
Preparing a 3 mol/L hydrochloric acid solution, pouring the annealed nitrogen-doped amorphous carbon shell coated zinc oxide powder into the prepared hydrochloric acid solution, etching for 3 hours, and centrifugally drying to obtain the nitrogen-doped hollow carbon shell.
Example 4
A preparation method of a nitrogen-doped hollow amorphous carbon shell sodium metal battery negative electrode material comprises the following steps:
(1) zinc oxide nano rod
The zinc oxide nano rod is synthesized by a water bath method.
The preparation steps are as follows: adding zinc acetate dihydrate (C) 4 H 6 O 4 ·Zn·2H 2 O, 1.1 g), hexamethylenetetramine (C) 6 H 12 N 4 0.7 g) of zinc oxide powder is dissolved in 200 ml of deionized water, heated for 5 hours in a water bath at the temperature of 90 ℃, and centrifugally dried to obtain white zinc oxide powder.
(2) Preparation of nitrogen-doped hollow amorphous carbon shell
220 mg dopamine hydrochloride was dissolved in 74 ml alcohol and 34 ml deionized water, 170 mg Tris was dissolved in 8 ml alcohol and 4 ml deionized water, after which Tris buffer was slowly added dropwise to the dopamine hydrochloride solution. Pouring the zinc oxide powder in the step (1) into the solution, and stirring for 12 hours in the dark. And then centrifugally drying, and annealing for 5 hours at 800 ℃ in an argon atmosphere to obtain the zinc oxide coated by the nitrogen-doped amorphous carbon shell.
Preparing 4 mol/L hydrochloric acid solution, pouring the annealed zinc oxide powder coated by the nitrogen-doped amorphous carbon shell into the prepared hydrochloric acid solution, etching for 2.5 hours, and centrifugally drying to obtain the nitrogen-doped hollow carbon shell.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A preparation method of a nitrogen-doped hollow amorphous carbon shell sodium metal battery cathode material is characterized by comprising the following steps: slowly dripping a Tris buffer into a dopamine hydrochloride solution, adding a zinc oxide nanorod, stirring, centrifugally drying, annealing in an argon atmosphere to obtain a nitrogen-doped amorphous carbon shell coated zinc oxide material, and etching with hydrochloric acid to obtain a nitrogen-doped hollow carbon shell material with the length of 3-4 mu m and the diameter of 400 nm;
the preparation method of the nitrogen-doped hollow amorphous carbon shell sodium metal battery cathode material comprises the following specific steps:
(1) preparing zinc oxide nanorod powder;
(2) respectively dissolving Tris and dopamine hydrochloride in a solvent, and then slowly dropwise adding a Tris buffer solution into a dopamine hydrochloride solution;
(3) adding zinc oxide nanorod powder into the mixed solution obtained in the step (2), and stirring for 12 hours in a dark environment;
(4) centrifugally drying the solution obtained in the step (3), and annealing to obtain nitrogen-doped amorphous carbon shell coated zinc oxide powder;
(5) and (5) putting the powder obtained in the step (4) into a prepared hydrochloric acid solution for etching to obtain the nitrogen-doped hollow amorphous carbon shell material.
2. The preparation method according to claim 1, wherein the zinc oxide nanorod powder in the step (1) is prepared by the following steps: dissolving zinc acetate dihydrate and hexamethylenetetramine in deionized water, heating in a water bath for reaction, and centrifugally drying the obtained white solution to obtain white zinc oxide powder.
3. The method of claim 2, wherein: the mass ratio of the zinc acetate dihydrate to the hexamethylenetetramine to the deionized water is 1.1: 0.7: 200, heating in water bath at 90 deg.c for 5 hr.
4. The method of claim 1, wherein: the solvent in the step (2) is a mixed solvent of alcohol and deionized water; the mass ratio of the dopamine hydrochloride, the alcohol and the deionized water is (110- & lt 120- & gt): 37: 17; the mass ratio of the Tris buffer to the alcohol to the deionized water is (40-45): 2: 1, the volume ratio of the dopamine hydrochloride solution to the Tris buffer solution is (27-30): 3.
5. the method of claim 1, wherein: the mass ratio of the mixed solution to the zinc oxide nanorod powder in the step (3) is 100: (0.1-1).
6. The method of claim 1, wherein: the annealing treatment in the step (4) is performed under the condition of argon at the temperature of 600-800 ℃ for 4-6 hours.
7. The method of claim 1, wherein: in the step (5), the concentration of hydrochloric acid is 3-5 mol/l, and the etching time is 2-3 hours.
8. The nitrogen-doped hollow amorphous carbon shell material prepared by the preparation method of any one of claims 1 to 7, which is characterized in that: the nitrogen-doped hollow amorphous carbon shell material is a rod-shaped hollow structure with the length of 3-4 mu m and the diameter of 400 nm.
9. The use of the nitrogen-doped hollow amorphous carbon shell material of claim 8 in the negative electrode material of sodium metal batteries.
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