CN109817933B - Carbon-based composite iron cyanamide material, preparation method thereof and sodium ion battery adopting carbon-based composite iron cyanamide material as negative electrode material - Google Patents
Carbon-based composite iron cyanamide material, preparation method thereof and sodium ion battery adopting carbon-based composite iron cyanamide material as negative electrode material Download PDFInfo
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Abstract
The invention discloses a preparation method of a carbon-based composite cyanamide iron material, which comprises the following steps of (0.1-1) fully grinding and mixing ferric oxalate ferrylamine, urea and conductive carbon according to the mass ratio of 1:2 to obtain uniform mixture powder, wherein the product is marked as A; adding a surfactant into the product A, dissolving in water, dispersing, and performing freeze drying to obtain a black product B; pyrolyzing the product B in a protective atmosphere to obtain a product C, namely a carbon-based composite iron cyanamide material; taking the obtained carbon-based composite iron cyanamide material as a negative electrode material of the sodium-ion battery; the invention adopts a high-temperature pyrolytic nitridation method to convert FeCN into FeCN2The composite material is compounded with conductive carbon, the synthesized product carbon-coated iron cyanamide active material is used as a negative electrode material of a sodium ion battery, a new material system is constructed by adding the conductive carbon material, the conductivity of the material is favorably enhanced, the preparation method is simple to operate, low in cost, safe and nontoxic, and the industrial production is expected to be realized.
Description
Technical Field
The invention belongs to the technical field of electrochemical materials, and particularly relates to a carbon-based composite iron cyanamide material and a preparation method thereof, and a sodium ion battery adopting the material.
Background
In recent years, due to the increasing urgency of the utilization of renewable energy sources for the demand of large-scale energy storage technology, sodium ion batteries with cheap resources are receiving extensive attention from the scientific and industrial fields. However, because the size of sodium ions is large (DNa + ═ 0.106nm, DLi + ═ 0.076nm), the sodium ions are difficult to be directly embedded into electrode materials of many sodium ion batteries to realize an electrochemical sodium storage process, and the application prospect of the batteries is greatly limited. Therefore, how to take charge-discharge rate and sodium storage capacity of the electrode material of the sodium ion battery into consideration has become a research hotspot direction of many scholars in recent years, and the regulation of the charge-discharge mechanism of the battery and the search of a new material structural system are considered to be the key points for solving the problems. Carbodiimide transition metal salt (MNCN, M is transition metal) is a sodium ion battery cathode material with high charge-discharge capacity potential, but the material is difficult to obtain directly and the composite structure of the material is difficult to obtain, so that the application of the material is obviously limited. If the high-conductivity material can be directly constructed and compounded with the high-conductivity material in one step by the technology of the invention to improve the conductivity of the material and relieve the volume expansion generated when sodium ions are embedded and removed by surface coating, the application of the material in the field of battery electrode materials is expected to be popularized.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for in-situ growth of a carbon/iron cyanamide composite structure on the surface of a carbon substrate as a sodium ion battery cathode material, a new material system is constructed by adding a conductive carbon material, the conductivity of the material is favorably enhanced, and the preparation method is simple to operate, low in cost, safe and nontoxic, and is expected to realize industrial production.
In order to achieve the purpose, the invention adopts the technical scheme that the preparation method of the carbon-based composite iron cyanamide material comprises the following steps:
step 2, adding a surfactant into the product A, wherein the mass ratio of the surfactant to ferric ammonium oxalate in the product A is 1 (0.02-0.05), dissolving in water, dispersing, and freezing and drying to obtain a black product B;
step 3, pyrolyzing the product B in a protective atmosphere to obtain a product C, namely the carbon-based composite iron cyanamide material; in the step, the product B is pyrolyzed in a tube furnace, the temperature is raised from room temperature to 160 ℃ at the speed of 30 ℃/min, the temperature is kept for 1h, and then the temperature is continuously raised to 600 ℃ at the temperature raising speed of 5 ℃/min-10 ℃/min.
As an alternative, in the step 1, analytically pure ferric ammonium oxalate, urea and conductive carbon are respectively taken according to the mass ratio of 1:2: 0.5.
The conductive carbon in the step 1 is CNT, graphene or super-p.
In the step 2, the surfactant is EDTA, ethanolamine, ethylamine, oleic acid, oleylamine or CTAB.
And 2, adopting ultrasonic dispersion, wherein the ultrasonic power is 300W, and the ultrasonic duration is 10-90 min.
And in the step 2, freeze-drying, namely placing the product in a watch glass, dispersing the product in water, placing the product in a freezing trap of a freeze dryer until the temperature of the sample in the watch glass reaches-50 ℃, completely freezing the product into a solid state for 12-24 hours, and vacuumizing the product to sublimate water until the water in the product is completely removed.
The carbon-based composite iron cyanamide material is prepared by the preparation method.
The invention also discloses a sodium ion battery, and the carbon-based composite iron cyanamide material is used as a negative electrode material of the sodium ion battery.
Compared with the prior art, the invention has at least the following beneficial effects: the invention adopts a high-temperature pyrolytic nitridation method to convert FeCN into FeCN2Compounding with conductive carbon, synthesizing product carbon-coated iron cyanamide active material as negative electrode material of sodium ion battery, and coating conductive carbon in FeCN2The surface is uniformly coated or the particles are uniformly dispersed on the surface, the conductive carbon is a polymer material with a unique structure, the specific surface area is large, the conductivity is good, and FeC can be enhancedN2When the surfactant is added to enhance the dispersibility of the conductive carbon, the appearance distribution of the sample is more uniform, the structure of the iron-carbon diimine and conductive carbon composite material is regulated and controlled, and the conductivity and the cycle reversibility of the composite material are improved; the exposed area of the conductive carbon can be larger, so that FeCN (FeCN)2The particles have larger attachment area, so that the growth chance is larger, and the rate capability is improved; the invention is safe and nontoxic, has low cost and simple and convenient operation.
Furthermore, the surface of the carbon substrate can be effectively activated and activated growth sites can be formed by heat preservation for 1h at 160 ℃; the proper temperature rising rate is kept to realize the uniform reaction of the urea and the raw materials, so that the side reaction is avoided; the proper heat preservation temperature is adopted to ensure that the iron cyanamide can be nucleated and grown on the surface of the carbon-based composite material uniformly, excessive byproducts are not generated, and the generation of products can be realized at a higher speed.
Drawings
FIG. 1 is an SEM photograph of example 1 of the present invention, in which (a) is a low magnification view and (b) is a high magnification view.
Figure 2 is an XRD pattern of example 1 of the present invention.
FIG. 3 is a graph of electrochemical performance of example 2 of the present invention.
Detailed Description
The invention is explained and illustrated in detail below with reference to the figures and examples.
Example 1
The carbon-based composite iron cyanamide material is prepared by the following steps:
1) taking 1g of analytically pure ferric ammonium oxalate, 2g of urea and 0.1g of CNT according to the mass ratio of 1:2:0.1, and fully grinding in a glass mortar to obtain fine and uniform light green mixture powder, wherein the product is marked as A;
2) adding 0.02g of EDTA into the product A, dissolving in water, performing ultrasonic dispersion for 10min, and then putting into a freeze dryer, and drying at-50 ℃ for 12h to obtain a completely dried black product B;
3) and putting the product B into a ceramic crucible, putting the ceramic crucible into a tubular furnace, pyrolyzing the product B in an argon atmosphere, heating the product B from room temperature to 160 ℃ at the speed of 30 ℃/min, preserving the heat for 1h, and then continuously keeping the temperature to 400 ℃ at the heating speed of 5 ℃/min to obtain the product, namely the carbon-based composite iron cyanamide material.
When the obtained product was observed by a scanning electron microscope of JSM-6700F type manufactured by Japan K.K., it was found that many cracks were formed on the surface of the product as seen from SEM images of FIG. 1(a) and FIG. 1(b), and a large number of CNTs having a linear structure were clearly observed in the cracks, and spherical small particles having a diameter of about 50nm and being uniformly distributed were clearly seen, and the CNTs were relatively uniformly grown in the matrix. The obtained product particles are analyzed by a Japanese science D/max2000 PCX-ray diffractometer to obtain a sample, and the product is FeCN2As shown in fig. 2.
Example 2
The carbon-based composite iron cyanamide material is prepared by the following steps:
1) taking 1.5g of analytically pure ferric ammonium oxalate, 3g of urea and 0.45g of graphene according to the mass ratio of 1:2:0.3, placing the materials in a glass mortar, and fully grinding the materials to obtain fine and uniform light green mixture powder, wherein the product is marked as A;
2) adding 0.045g of ethanolamine into the product A, dissolving in water, performing ultrasonic dispersion for 30min, then putting into a freeze dryer, and drying at-50 ℃ for 16h to obtain a completely dried black product B;
3) and putting the product B into a ceramic crucible, putting the ceramic crucible into a tubular furnace, pyrolyzing the product B in an argon atmosphere, heating the product B from room temperature to 160 ℃ at the speed of 30 ℃/min, preserving the heat for 1h, and then continuously keeping the temperature to 600 ℃ at the heating speed of 6 ℃/min to obtain the product, namely the carbon-based composite iron cyanamide material.
The obtained product is prepared into a button type sodium ion battery, and the specific packaging steps are as follows: uniformly grinding active powder, a conductive agent (super-p) and a bonding agent (carboxymethyl cellulose CMC) according to the mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on a copper foil by using a film coating device, and drying for 12 hours in a vacuum drying oven at 80 ℃; then assembling the electrode plates into a sodium ion half cell, and carrying out cross current charging and discharging test on the cell by adopting a Xinwei electrochemical workstation, wherein the test voltage is 0.01-3.0V, and the test voltage isThe flow density is 0.1 and 0.5A g-1The test results are shown in fig. 3, and fig. 3 shows that the charge-discharge specific capacity is higher under low current density, the cycle performance is good, and the rate performance and the cycle stability are better.
Example 3
The carbon-based composite iron cyanamide material is prepared according to the following steps:
1) respectively taking 2g of analytically pure ferric ammonium oxalate, 4g of urea and 0.12g of super-p according to the mass ratio of 1:2:0.6, fully grinding and mixing in a glass mortar to obtain fine and uniform light green mixture powder, and marking the product as A;
2) adding 0.08g of oleic acid into the product A, dissolving in water, performing ultrasonic dispersion for 60min, then putting into a freeze dryer, and drying at-50 ℃ for 18h to obtain a completely dried black product B;
3) and putting the product B into a ceramic crucible, putting the ceramic crucible and the product B into a tubular furnace, pyrolyzing the product B in an argon atmosphere, heating the product B from room temperature to 160 ℃ at the speed of 30 ℃/min, preserving the heat for 1h, and then continuously keeping the temperature to 600 ℃ at the heating speed of 8 ℃/min to obtain the product, namely the carbon-based composite iron cyanamide material.
Example 4
The carbon-based composite iron cyanamide material is prepared according to the following steps:
1) respectively taking 1g of analytically pure ferric ammonium oxalate, 2g of urea and 1g of CNT (carbon nano tube) according to the mass ratio of 1:2:1, and fully grinding in a glass mortar to obtain fine and uniform light green mixture powder, wherein the product is marked as A;
2) adding 0.05g of CTAB into the product A, dissolving in water, performing ultrasonic dispersion for 60min, then putting into a freeze dryer, and drying at-50 ℃ for 24h to obtain a completely dried black product B;
3) and putting the product B into a ceramic crucible, putting the ceramic crucible into a tubular furnace, pyrolyzing the product B in an argon atmosphere, heating the product B from room temperature to 160 ℃ at the speed of 30 ℃/min, preserving the heat for 1h, and then continuously keeping the temperature to 600 ℃ at the heating speed of 10 ℃/min to obtain the product, namely the carbon-based composite iron cyanamide material.
Claims (6)
1. A preparation method of a carbon-based composite iron cyanamide material is characterized by comprising the following steps:
step 1, respectively taking ferric ammonium oxalate, urea and conductive carbon according to a mass ratio of 1:2 (0.1-1), fully grinding and mixing to obtain uniform mixture powder, and recording a product A;
step 2, adding a surfactant into the product A, dissolving the surfactant in water, dispersing the mixture, and performing freeze drying to obtain a black product B, wherein in the step 2, the mass ratio of ferric ammonium oxalate to the surfactant in the product A is 1 (0.02-0.05); the surfactant is EDTA, ethanolamine, ethylamine, oleic acid, oleylamine or CTAB;
step 3, pyrolyzing the product B in a protective atmosphere to obtain a product C, namely the carbon-based composite iron cyanamide material;
the pyrolysis is to pyrolyze the product B in a tube furnace, raise the temperature from room temperature to 160 ℃ at the rate of 30 ℃ per minute, preserve the temperature for 1h, and then continue to keep raising the temperature to 400 ℃ at the rate of raising the temperature of 5 ℃ per minute-10 ℃ per minute;
the conductive carbon in step 1 is CNT; the CNT is linear, and the CNT is grown in the matrix.
2. The method for preparing the carbon-based composite iron cyanamide material according to claim 1, wherein in the step 1, analytically pure ferric ammonium oxalate, urea and conductive carbon are respectively taken according to a mass ratio of 1:2: 0.5.
3. The method for preparing the carbon-based composite iron cyanamide material according to claim 1, wherein ultrasonic dispersion is adopted in the step 2, the ultrasonic power is 300W, and the ultrasonic duration is 10min to 90 min.
4. The method for preparing the carbon-based composite iron cyanamide material according to claim 1, wherein the step 2 of dissolving in water and then dispersing is carried out by placing the mixture in a watch glass and dispersing in water, and the freeze drying is carried out by placing the watch glass in a freezing trap of a freeze dryer until the temperature of the sample in the watch glass reaches-50 ℃, completely freezing the sample into a solid state for 12-24h, and vacuumizing the freeze drying to sublimate the water until the water in the product is completely removed.
5. A carbon-based composite iron cyanamide material obtained by the preparation method of any one of claims 1 to 4.
6. A sodium ion battery, characterized in that the negative electrode material of the battery adopts the carbon-based composite iron cyanamide material of claim 5.
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| CN113224302B (en) * | 2021-05-08 | 2022-08-05 | 陕西科技大学 | Iron cyanamide material for realizing graphitized carbon coating by in-situ autocatalysis and application thereof |
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