CN115425209A - Preparation method and application of myrica-shaped iron-doped cobalt-based chalcogenide nitrogen-doped carbon porous composite material - Google Patents

Preparation method and application of myrica-shaped iron-doped cobalt-based chalcogenide nitrogen-doped carbon porous composite material Download PDF

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CN115425209A
CN115425209A CN202211186912.3A CN202211186912A CN115425209A CN 115425209 A CN115425209 A CN 115425209A CN 202211186912 A CN202211186912 A CN 202211186912A CN 115425209 A CN115425209 A CN 115425209A
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cobalt
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iron
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杨叶锋
胡佳佳
温仪
姚珠君
蔡晨
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Zhejiang Sci Tech University ZSTU
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Abstract

The invention relates to the field of sodium ion batteries, and discloses a preparation method and application of a myrica-shaped iron-doped cobalt-based chalcogenide nitrogen-doped carbon porous composite material, wherein zinc salt, iron salt, F127, PVP and potassium cobalt cyanide are used as raw materials to perform normal-temperature precipitation reaction to generate a FeZnCo-PBA precursor; and carrying out heat treatment under a protective atmosphere, and then further carrying out gas-phase sulfur (selenium) conversion with sulfur powder or selenium powder to obtain the iron-doped cobalt-based chalcogenide nitrogen-doped carbon porous composite material. The invention organically combines a plurality of means to relieve the volume expansion effect of the cobalt-based chalcogenide in the charge-discharge process and improve the conductivity of the cobalt-based chalcogenide, so that the composite material has long cycle life and good electrochemical performance when being used as a cathode material of a sodium ion battery.

Description

Preparation method and application of myrica-shaped iron-doped cobalt-based chalcogenide nitrogen-doped carbon porous composite material
Technical Field
The invention relates to the field of sodium ion batteries, in particular to a preparation method and application of a myrica-shaped iron-doped cobalt-based chalcogenide nitrogen-doped carbon porous composite material.
Background
In the present day that fossil energy is continuously consumed and tends to be exhausted, the search for alternative clean energy is a key problem which needs to be solved for the long time in human development and the ecological environment of the earth. Among them, the development of efficient and stable energy storage and conversion means is the current and future research hotspot. However, the very limited lithium resources limit the wide-spread use of lithium ion batteries today. The sodium ion battery has similar energy storage mechanism with the lithium ion battery, rich sodium resource and low acquisition cost, and has received extensive attention of researchers in recent years. Since the radius of sodium ions is larger than that of lithium ions, sodium ions tend to occupy interstitial sites with more space during intercalation. Therefore, the search for suitable sodium insertion host materials is the key to the development of sodium ion batteries.
As a conversion type sodium storage material, cobalt-based chalcogenide attracts attention of researchers due to the characteristics of higher theoretical specific capacity, narrower forbidden band width than oxide, easier breakage of metal-S (Se) bond than metal-O bond, higher first-turn efficiency and the like. However, irreversible volume changes generated in the electrochemical reaction process can cause agglomeration and pulverization phenomena of the electrode, thereby shortening the service life of the electrode. Secondly, there are slow diffusion kinetics as electrode materials, which limits the large-scale application of cobalt-based chalcogenide electrodes.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method and application of a waxberry-shaped iron-doped cobalt-based chalcogenide nitrogen-doped carbon porous composite material. The invention organically combines a plurality of means to relieve the volume expansion effect of the cobalt-based chalcogenide in the charge-discharge process and improve the conductivity of the cobalt-based chalcogenide, so that the composite material has long cycle life and good electrochemical performance when being used as a cathode material of a sodium ion battery.
The specific technical scheme of the invention is as follows:
in a first aspect, the invention provides a preparation method of a myrica-shaped iron-doped cobalt-based chalcogenide nitrogen-doped carbon porous composite material, which comprises the following steps:
(1) Adding zinc salt, iron salt, polyvinylpyrrolidone (PVP) and Pluronic F-127 (F127) into water, and stirring uniformly to obtain a yellow transparent solution A.
(2) And (3) ultrasonically dissolving potassium cobalt cyanide in water to obtain a transparent solution B, and dripping the transparent solution B into the yellow transparent solution A under the condition of continuous stirring to form a yellow transparent solution C.
(3) And (3) placing the transparent solution C obtained in the step (2) in an ice water bath for ultrasonic treatment to obtain a suspension C.
(4) And (4) standing the suspension C obtained in the step (3), and then washing and drying the suspension C to obtain light yellow powder alpha, namely Yang Meizhuang FeZnCo-PBA precursor.
(5) And (5) carrying out heat treatment on the light yellow powder alpha obtained in the step (4) in a protective atmosphere to obtain black powder beta, namely the iron/cobalt/carbon composite material.
(6) And (3) carrying out heat treatment on the black powder beta obtained in the step (5) and sulfur powder or selenium powder under the protection of inert gas to obtain black powder gamma, namely Yang Meizhuang iron-doped cobalt disulfide/nitrogen-doped carbon porous composite material or waxberry-shaped iron-doped cobalt diselenide/nitrogen-doped carbon porous composite material.
In the above step, the reactions mainly take place as follows: firstly, metal ions react with cobalt cyanide to generate FeZnCo-PBA Prussian blue, wherein PVP is used for preventing the zinc-iron metal ions from reacting with the cobalt cyanide too fast; then carrying out high-temperature carbonization treatment on the precursor, carrying out pore-forming after zinc is sublimated and lost in the process, simultaneously carrying out reaction decomposition on F127 and PVP to obtain carbon, and obtaining metal cobalt under the reduction of the carbon to obtain the iron-doped cobalt metal nitrogen-doped carbon spheres; and finally, carrying out vulcanization (selenization) treatment on the cobalt to obtain the iron-doped cobalt disulfide (cobalt diselenide)/nitrogen-doped carbon porous composite material, wherein the cobalt is vulcanized (selenized) into cobalt disulfide (cobalt diselenide), the material presents waxberry-shaped appearance and porous structural characteristics, and the particle size is about 0.5-0.9 mu m.
The present inventors have found that when a cobalt-based chalcogenide is directly compounded with a carbon material or carbon-coated with the cobalt-based chalcogenide, the interface coupling therebetween is weak, and the two are easily exfoliated and separated, thereby leading to a reduction in cycle life. For this reason, the present invention solves the technical problem by the following aspects:
for the first time, feZnCo-PBA with uniform particles is selected as a precursor, a stable Prussian blue framework structure is introduced under the combined action of a structure directing agent PVP and a porous template F127, and a carbon framework obtained after heat treatment provides a continuous conductive network for cobalt-based chalcogenide, so that the integral structural stability of the composite material can be improved. Compared with the reported ordinary cubic Prussian blue framework structure, the FeZnCo-PBA is waxberry-shaped, and compared with the ordinary cubic Prussian, the waxberry-shaped Prussian blue framework structure has the advantages of more stable structure, larger specific surface area and easier release of volume expansion.
Secondly, the porous carbon layer in the invention relieves the volume expansion effect generated during the charge and discharge of the cobalt-based chalcogenide; the porous structure derived from FeZnCo-PBA effectively increases the contact area of the active substance and the electrolyte, provides abundant active sites and transmission pore channels, and promotes ion migration. Due to the introduction of iron ions, part of the iron ions replace the positions of cobalt ions, and the electronic conductivity of cobalt disulfide (cobalt diselenide) is further improved through synergistic effect.
In addition, the invention widens the charge transmission path by utilizing the synergistic action of the nitrogen-doped carbon substrate, and can further improve the charge diffusion rate.
In conclusion, compared with other types of porous carbon frames, the porous carbon frame material prepared by the invention has the advantages that the frame is firmer, the pore canals are more, not only zinc ions are sublimated to form pores, but also F127 serving as a pore-forming agent has the pore-forming capability; cyanogen in PVP and potassium cobalt cyanide is used as a nitrogen source, nitrogen doping is beneficial to enhancing the conductivity, F127 and PVP are used as carbon sources, and the carbon content is richer. The invention organically combines a plurality of means to relieve the volume expansion effect of the cobalt-based chalcogenide in the charge-discharge process and improve the conductivity of the cobalt-based chalcogenide, so that the composite material has long cycle life and good electrochemical performance when being used as a cathode material of a sodium ion battery.
Preferably, in steps (1) and (2),
Fe 3+ and Zn 2+ The molar ratio of the components is 1:15-1:3;
the mass ratio of PVP to Pluronic F-127 is 1.8:1-3.6:1;
the total molar ratio of the potassium cobalt cyanide to the metal ions is 4:5-2:3;
the mass ratio of the potassium cobalt cyanide to the PVP is 1:4-1:10.
To obtain a prussian blue structure in the form of myrica, the presence of zinc ions and the content of PVP and F127 are of crucial importance. Specifically, it is found that prussian blue structure formed by other metal salts (except zinc) and ferricyanide and cobalt cyanide is in a three-dimensional square shape, while prussian blue structure formed by zinc salts and ferricyanide and cobalt cyanide in combination with a proper amount of PVP is in a spherical shape, and on the basis of the three-dimensional square structure, a proper amount of F127 is additionally added to obtain a rough-surface myrica-like structure.
Preferably, in step (1), the zinc salt is a soluble zinc salt; the ferric salt is a trivalent ferric salt.
Preferably, in the step (1), the stirring time is 20-40 minutes; in the step (2), the stirring time is 5-20 minutes.
Preferably, in the step (3), the ice-water bath ultrasound is performed at 10 to 20 ℃ for 20 to 40 minutes.
Preferably, in the step (4), the standing time is 6 to 48 hours, and the standing temperature is 15 to 30 ℃.
Preferably, in the step (5), the heat treatment temperature is 600-1000 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time is 1-3 hours.
Preferably, in the step (6), the mass ratio of the iron/cobalt/carbon composite material to the sulfur powder or selenium powder is 1:2-1:5; the heat treatment temperature is 300-600 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time is 2-5 hours.
Preferably, in the step (5), the protective atmosphere for the heat treatment is nitrogen or argon-hydrogen; in the step (6), the protective atmosphere is nitrogen or argon.
In a second aspect, the invention provides an application of the myrica-shaped iron-doped cobalt-based chalcogenide nitrogen-doped carbon porous composite material as a sodium-ion battery negative electrode material.
Compared with the prior art, the invention has the beneficial effects that:
(1) The FeZnCo-PBA precursor with uniform particles is prepared by a normal-temperature precipitation method, the preparation method is simple and convenient, the reaction condition is simple, the appearance size is controllable, a stable myrica Prussian blue frame structure is formed under the combined action of a structure directing agent PVP and a porous template F127, a carbon frame obtained after heat treatment provides a continuous conductive network for cobalt disulfide (cobalt diselenide), and the integral structural stability of the composite material is improved.
(2) The myrica-shaped iron-doped cobalt disulfide/nitrogen-doped carbon porous composite material or the iron-doped cobalt diselenide/nitrogen-doped carbon porous composite material prepared by the invention is used as a sodium ion battery cathode material, wherein a porous carbon layer relieves the volume expansion effect generated during the charge and discharge of cobalt disulfide (cobalt diselenide); and the contact area of the active substance and the electrolyte is effectively increased, rich active sites and transmission pore channels are provided, the transmission path of sodium ions is shortened, and the connection effect is enhanced. Due to the introduction of iron ions, a part of iron ions replace the positions of cobalt ions, the electronic conductivity of cobalt disulfide (cobalt diselenide) is further improved through the synergistic effect, and in addition, the charge transmission path is improved by utilizing the synergistic effect of a nitrogen-doped carbon matrix, and the charge diffusion rate is maintained.
(3) The invention organically combines a plurality of means to relieve the volume expansion effect of the cobalt-based sulfide (selenide) compound in the charging and discharging process and improve the conductivity of the cobalt-based sulfide (selenide) compound, so that the composite material has long cycle life and good electrochemical performance as the cathode material of the sodium ion battery.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of the myrica iron-doped cobalt disulfide/nitrogen-doped carbon porous composite prepared in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the FeZnCo-PBA precursor prepared in example 1;
fig. 3 is an SEM image of the myrica-like iron-doped cobalt disulfide/nitrogen-doped carbon porous composite prepared in example 2;
FIG. 4 is a Transmission Electron Micrograph (TEM) of the myrica-like iron-doped cobalt disulfide/nitrogen-doped carbon porous composite prepared in example 1;
fig. 5 is a battery cycle performance graph of the myrica-like iron-doped cobalt disulfide/nitrogen-doped carbon porous composite prepared in example 1;
fig. 6 is a battery rate performance graph of the myrica-like iron-doped cobalt disulfide/nitrogen-doped carbon porous composite material prepared in example 1;
fig. 7 is a battery cycle performance graph of the myrica-like iron-doped cobalt disulfide/nitrogen-doped carbon porous composite prepared in example 2;
fig. 8 is a battery rate performance graph of the myrica-like iron-doped cobalt disulfide/nitrogen-doped carbon porous composite prepared in example 3;
fig. 9 is an XRD pattern of the myrica-like iron-doped cobalt diselenide/nitrogen-doped carbon porous composite prepared in example 7.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
(1) 3mmol of zinc acetate, 0.6mmol of ferric chloride, 3.6g of PVP and 2g of F127 are mixed, stirred and dissolved in 100mL of deionized water, and stirring is continued for 30 minutes to obtain a yellow transparent solution A;
(2) Ultrasonically dissolving 2mmol of potassium cobalt cyanide in 100mL of deionized water, stirring to obtain a transparent solution B, dripping the solution B into the solution A prepared in the step (1) under the condition of continuous stirring, and stirring for 10 minutes to form a yellow transparent solution C;
(3) Carrying out ultrasonic treatment on the transparent solution C obtained in the step (2) for 15 minutes under the ice-water bath condition to obtain a suspension C;
(4) Standing the suspension C obtained in the step (3) for 24 hours, performing centrifugal separation to obtain a yellow product, washing the yellow product with deionized water and absolute ethyl alcohol for three times, drying the yellow product in a vacuum oven at the temperature of 80 ℃ for 12 hours to obtain light yellow powder alpha, wherein the light yellow powder alpha is a FeZnCo-PBA precursor;
(5) 0.2g of FeZnCo-PBA is placed in nitrogen atmosphere, the temperature is increased to 800 ℃ and calcined for 2 hours to obtain black powder beta, and the heating rate is 2 ℃ for min -1 I.e., iron/cobalt/carbon composites;
(6) Weighing 0.2g of sulfur powder and 0.05g of black iron/cobalt/carbon composite material, respectively locating the sulfur powder and the black iron/cobalt/carbon composite material at the upstream and downstream of a tube furnace, and carrying out reaction at 2 ℃ for min in a nitrogen atmosphere -1 The temperature rise rate is increased to 500 ℃ and the mixture is calcined for 4 hours to obtain black powder gamma, namely Yang Meizhuang iron-doped cobalt disulfide/nitrogen-doped carbon porous composite material.
Example 2
(1) 1.44mmol of zinc chloride, 0.36mmol of ferric chloride, 1.8g of PVP and 0.2g of F127 are mixed, stirred and dissolved in 50mL of deionized water, and stirring is continued for 30 minutes to obtain a yellow transparent solution A;
(2) Ultrasonically dissolving 1mmol of potassium cobalt cyanide in 50mL of deionized water, stirring to obtain a transparent solution B, dripping the solution B into the solution A prepared in the step (1) under the condition of continuous stirring, and stirring for 10 minutes to form a yellow transparent solution C;
(3) Carrying out ultrasonic treatment on the transparent solution C obtained in the step (2) for 15 minutes under the ice-water bath condition to obtain a suspension C;
(4) Standing the suspension C obtained in the step (3) for 24 hours, performing centrifugal separation to obtain a yellow product, washing the yellow product with deionized water and absolute ethyl alcohol for three times, drying the yellow product in a vacuum oven at the temperature of 80 ℃ for 12 hours to obtain light yellow powder alpha, wherein the light yellow powder alpha is a FeZnCo-PBA precursor;
(5) 0.2g of FeZnCo-PBA is placed in nitrogen atmosphere, the temperature is increased to 800 ℃ and calcined for 2 hours to obtain black powder beta, and the heating rate is 2 ℃ for min -1 I.e., iron/cobalt/carbon composites;
(6) Weighing 0.2g of sulfur powder and 0.05g of black iron/cobalt/carbon composite material, respectively locating the sulfur powder and the black iron/cobalt/carbon composite material at the upstream and downstream of a tube furnace, and carrying out reaction at 2 ℃ for min in a nitrogen atmosphere -1 The temperature rise rate is increased to 500 ℃ and the mixture is calcined for 4 hours to obtain black powder gamma, namely Yang Meizhuang iron-doped cobalt disulfide/nitrogen-doped carbon porous composite material.
Example 3
(1) 1.6mmol of zinc acetate, 0.2mmol of ferric nitrate, 1.8g of PVP and 0.6g of F127 are mixed, stirred and dissolved in 50mL of deionized water, and stirring is continued for 30 minutes to obtain a yellow transparent solution A;
(2) Ultrasonically dissolving 1mmol of potassium cobalt cyanide in 50mL of deionized water, stirring to obtain a transparent solution B, dripping the solution B into the solution A prepared in the step (1) under the condition of continuous stirring, and stirring for 10 minutes to form a yellow transparent solution C;
(3) Carrying out ultrasonic treatment on the transparent solution C obtained in the step (2) for 17 minutes under the ice-water bath condition to obtain a suspension C;
(4) Standing the suspension C obtained in the step (3) for 24 hours, performing centrifugal separation to obtain a yellow product, washing the yellow product with deionized water and absolute ethyl alcohol for three times, drying the yellow product in a vacuum oven at the temperature of 80 ℃ for 12 hours to obtain light yellow powder alpha, wherein the light yellow powder alpha is a FeZnCo-PBA precursor;
(5) Placing 0.2g FeZnCo-PBA in nitrogen atmosphere, heating to 1000 deg.C, calcining for 1 hr to obtain black powder beta, and heating at rate of 5 deg.C for min -1 I.e., iron/cobalt/carbon composites;
(6) Weighing 0.2g of sulfur powder and 0.05g of black iron/cobalt/carbon composite material, respectively locating the sulfur powder and the black iron/cobalt/carbon composite material at the upstream and downstream of a tube furnace, and carrying out reaction at 2 ℃ for min in a nitrogen atmosphere -1 The temperature rise rate is increased to 500 ℃ and the mixture is calcined for 4 hours to obtain black powder gamma, namely Yang Meizhuang iron-doped cobalt disulfide/nitrogen-doped carbon porous composite material.
Example 4
(1) 1.5mmol of zinc acetate, 0.3mmol of ferric chloride, 1.8g of PVP and 1g of F127 are mixed, stirred and dissolved in 50mL of deionized water, and stirring is continued for 30 minutes to obtain a yellow transparent solution A;
(2) Ultrasonically dissolving 1mmol of potassium cobalt cyanide in 50mL of deionized water, stirring to obtain a transparent solution B, dripping the solution B into the solution A prepared in the step (1) under the condition of continuous stirring, and stirring for 10 minutes to form a yellow transparent solution C;
(3) Performing ultrasonic treatment on the transparent solution C obtained in the step (2) for 18 minutes under the ice-water bath condition to obtain a suspension C;
(4) Standing the suspension C obtained in the step (3) for 24 hours, performing centrifugal separation to obtain a yellow product, washing the yellow product with deionized water and absolute ethyl alcohol for three times, drying the yellow product in a vacuum oven at the temperature of 80 ℃ for 12 hours to obtain light yellow powder alpha, wherein the light yellow powder alpha is a FeZnCo-PBA precursor;
(5) Placing 0.2g of FeZnCo-PBA in argon-hydrogen atmosphere, heating to 800 ℃, calcining for 2 hours to obtain black powder beta, wherein the heating rate is 2 ℃ min -1 I.e., iron/cobalt/carbon composites;
(6) Weighing 0.1g of sulfur powder and 0.05g of black iron/cobalt/carbon composite material, respectively locating the sulfur powder and the black iron/cobalt/carbon composite material at the upstream and downstream of a tube furnace, and carrying out reaction at 2 ℃ for min in a nitrogen atmosphere -1 The temperature rise rate is increased to 500 ℃, and the black powder gamma is obtained after calcining for 2 hours, namely the Yang Meizhuang iron-doped cobalt disulfide/nitrogen-doped carbon porous composite material.
Example 5
(1) 1.5mmol of zinc acetate, 0.3mmol of ferric chloride, 1.8g of PVP and 1g of F127 are mixed, stirred and dissolved in 50mL of deionized water, and stirring is continued for 30 minutes to obtain a yellow transparent solution A;
(2) Ultrasonically dissolving 2mmol of potassium cobalt cyanide in 50mL of deionized water, stirring to obtain a transparent solution B, dripping the solution B into the solution A prepared in the step (1) under the condition of continuous stirring, and stirring for 15 minutes to form a yellow transparent solution C;
(3) Carrying out ultrasonic treatment on the transparent solution C obtained in the step (2) for 30 minutes under the ice-water bath condition to obtain a suspension C;
(4) Standing the suspension C obtained in the step (3) for 24 hours, performing centrifugal separation to obtain a yellow product, washing the yellow product with deionized water and absolute ethyl alcohol for three times, drying the yellow product in a vacuum oven at the temperature of 80 ℃ for 12 hours to obtain light yellow powder alpha, wherein the light yellow powder alpha is a FeZnCo-PBA precursor;
(5) Placing 0.2g FeZnCo-PBA in nitrogen atmosphere, heating to 1000 deg.C, calcining for 1 hr to obtain black powder beta, and heating at rate of 5 deg.C for min -1 I.e., iron/cobalt/carbon composites;
(6) Weighing 0.2g of sulfur powder and 0.05g of black iron/cobalt/carbon composite material, respectively locating the sulfur powder and the black iron/cobalt/carbon composite material at the upstream and downstream of a tube furnace, and carrying out reaction at 3 ℃ for min in a nitrogen atmosphere -1 Rate of temperature rise ofCalcining at 400 ℃ for 4 hours to obtain black powder gamma, namely Yang Meizhuang iron-doped cobalt disulfide/nitrogen-doped carbon porous composite material.
Example 6
(1) 1.5mmol of zinc acetate, 0.3mmol of ferric chloride, 1.8g of PVP and 0.6g of F127 are mixed, stirred and dissolved in 50mL of deionized water, and stirring is continued for 30 minutes to obtain a yellow transparent solution A;
(2) Ultrasonically dissolving 2mmol of potassium cobalt cyanide in 50mL of deionized water, stirring to obtain a transparent solution B, dripping the solution B into the solution A prepared in the step (1) under the condition of continuous stirring, and stirring for 5 minutes to form a yellow transparent solution C;
(3) Carrying out ultrasonic treatment on the transparent solution C obtained in the step (2) for 15 minutes under the ice-water bath condition to obtain a suspension C;
(4) Standing the suspension C obtained in the step (3) for 24 hours, performing centrifugal separation to obtain a yellow product, washing the yellow product with deionized water and absolute ethyl alcohol for three times, drying the yellow product in a vacuum oven at the temperature of 80 ℃ for 12 hours to obtain light yellow powder alpha, wherein the light yellow powder alpha is a FeZnCo-PBA precursor;
(5) 0.2g of FeZnCo-PBA is placed in nitrogen atmosphere, the temperature is increased to 800 ℃ and calcined for 2 hours to obtain black powder beta, and the heating rate is 2 ℃ for min -1 I.e., iron/cobalt/carbon composites;
(6) Weighing 0.1g of sulfur powder and 0.05g of black iron/cobalt/carbon composite material, respectively locating the sulfur powder and the black iron/cobalt/carbon composite material at the upstream and downstream of a tubular furnace, and carrying out reaction at 3 ℃ for min in argon-hydrogen atmosphere -1 The temperature is raised to 400 ℃ at the temperature raising rate, and the black powder gamma is obtained after calcining for 4 hours, namely the Yang Meizhuang iron-doped cobalt disulfide/nitrogen-doped carbon porous composite material.
Example 7
(1) 1.5mmol of zinc acetate, 0.3mmol of ferric chloride, 1.8g of PVP and 0.8g of F127 are mixed, stirred and dissolved in 50mL of deionized water, and stirring is continued for 30 minutes to obtain a yellow transparent solution A;
(2) Ultrasonically dissolving 2mmol of potassium cobalt cyanide in 50mL of deionized water, stirring to obtain a transparent solution B, dripping the solution B into the solution A prepared in the step (1) under the condition of continuous stirring, and stirring for 10 minutes to form a yellow transparent solution C;
(3) Carrying out ultrasonic treatment on the transparent solution C obtained in the step (2) for 15 minutes under the ice-water bath condition to obtain a suspension C;
(4) Standing the suspension C obtained in the step (3) for 24 hours, performing centrifugal separation to obtain a yellow product, washing the yellow product three times by using deionized water and absolute ethyl alcohol, drying the yellow product in a vacuum oven at the temperature of 80 ℃ for 12 hours to obtain light yellow powder alpha, wherein the light yellow powder alpha is a FeZnCo-PBA precursor;
(5) 0.2g of FeZnCo-PBA is placed in nitrogen atmosphere, the temperature is increased to 800 ℃ and calcined for 2 hours to obtain black powder beta, and the heating rate is 2 ℃ for min -1 I.e., iron/cobalt/carbon composites;
(6) Weighing 0.2g of selenium powder and 0.05g of black iron/cobalt/carbon composite material, respectively locating at the upstream and downstream of a tube furnace, and carrying out nitrogen atmosphere at 2 ℃ for min -1 The temperature rise rate is increased to 400 ℃, and the black powder gamma is obtained after calcining for 2 hours, namely the Yang Meizhuang iron-doped cobalt diselenide/nitrogen-doped carbon porous composite material.
Performance testing
And (3) uniformly mixing the iron-doped cobalt disulfide/nitrogen-doped carbon porous composite material or the iron-doped cobalt diselenide/nitrogen-doped carbon porous composite material obtained in the step (6) in the embodiment with a conductive agent Super P, a binder polyvinylidene fluoride (PVDF) and N-methylpyrrolidone (NMP) to obtain slurry, coating the slurry on a copper current collector, and drying to obtain the battery cathode. Using glass fiber as a separator, 1mol L -1 With NaPF 6 The button cell is assembled in a glove box filled with argon by taking sodium metal as a counter electrode as electrolyte with diethylene glycol dimethyl ether as a solute and taking the sodium metal as a solvent. And (3) carrying out constant current charge and discharge test on the assembled sodium ion battery after the assembled sodium ion battery is placed for 24 hours, testing the capacity, the rate performance and the charge and discharge cycle performance of the negative electrode of the sodium ion battery in an environment of 25 +/-1 ℃ with a voltage window of 0.01V-3 v.
The maximum specific discharge capacities of the myrica-shaped iron-doped cobalt disulfide/nitrogen-doped carbon porous composite materials or the myrica-shaped iron-doped cobalt diselenide/nitrogen-doped carbon porous composite materials in the embodiments 1 to 7, which are assembled into a sodium ion battery as a sodium ion electrode material, at different current densities are shown in table 1:
TABLE 1
Figure BDA0003864169330000091
As can be seen from the table, changing the carbonization temperature has some effect on the performance of the electrode material, and the carbonization temperature may affect the graphitization degree and thus the volume expansion of the carbon skeleton during charging and discharging. While increasing or decreasing the iron ion concentration may reduce the performance of the electrode material to some extent and perform poorly at high currents, perhaps due to the optimal iron ion concentration (Zn) 2+ ∶Fe 3+ = 3-7: 1) is more favorable for the position of metal cobalt substituted by metal iron, so as to generate synergistic effect and improve the conductivity, and therefore, the performance of the electrode material is not good due to the increase or decrease of the concentration of iron ions. And after the last step of sulfurization is changed into selenization, the capacity of the material is obviously reduced, mainly because although CoSe is used 2 And CoS 2 The mechanism of sodium storage is similar, but the relative atomic mass of S is smaller than that of Se, so CoS 2 Has a theoretical sodium storage capacity higher than that of CoSe 2 。
Fig. 1 is an XRD spectrum of example 1, which shows that the phase is cobalt disulfide with better crystallinity, and the phase of cobalt disulfide is not changed by iron doping. FIG. 2 is an SEM image of the precursor of example 1, which shows that the FeZnCo-PBA precursor has a waxberry-like morphology, uniformly dispersed particles, and an average particle size of 0.5-0.9 μm; fig. 3 is an SEM image of example 2, and it can be seen that the iron-doped cobalt disulfide/nitrogen-doped carbon porous composite material has a waxberry-shaped morphology with a rougher surface, uniformly dispersed particles, and a slightly smaller average particle size than the precursor; FIG. 4 is a TEM image of example 1; it can be seen that the iron-doped cobalt disulfide/nitrogen-doped carbon porous composite material shows that cobalt disulfide particles are wrapped by a carbon layer to form a large carbon sphere together, so that the rough waxberry-shaped appearance is shown. FIG. 5 is a graph showing the cycle characteristics of the sodium-ion battery of example 1, from which it can be seen that the sodium-ion battery has a current density of 1Ag -1 The electrochemical performance is excellent, and 600mAh g is still kept after 300 cycles -1 Of the battery. FIG. 6 is a rate diagram of the sodium ion battery of example 1, sodiumThe ion battery is 0.2Ag -1 、0.5Ag -1 、1Ag -1 、2Ag -1 、5Ag -1 And return to 0.1Ag -1 The capacity of the current density is 713.4mAh g -1 、634.5mAh g -1 、616.5mAh g -1 、585.6mAh g -1 、493.3mAh g -1 And 712.4mAh g -1 And excellent rate performance is shown. FIG. 7 is a graph showing the cycle characteristics of the sodium-ion battery of example 2, from which it can be seen that the sodium-ion battery has a current density of 1Ag -1 Shows better electrochemical performance at the beginning of the cycle and has 500mAh g -1 After 150 cycles, the capacity begins to decay to 400mAh g -1 The stability still needs to be improved; FIG. 8 is a rate graph of a sodium ion battery in example 3; 0.2Ag -1 、0.5Ag -1 、1Ag -1 、2Ag -1 、5Ag -1 And return to 0.1Ag -1 The capacity of the current density is 670.9mAh g -1 、608.6mAh g -1 、607.7mAh g -1 、520.3mAh g -1 、400.8mAh g -1 And 665.7mAh g -1 The better rate performance is shown, but the electrochemical performance of the examples 2 and 3 is lower than the best sample, which shows that the doping of the iron has the best doping ratio. Fig. 9 is an XRD spectrum of example 7, which shows that the phase is cobalt diselenide with better crystallinity, and the iron doping does not change the phase of cobalt diselenide.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (10)

1. A preparation method of a waxberry-shaped iron-doped cobalt-based chalcogenide nitrogen-doped carbon porous composite material is characterized by comprising the following steps of:
(1) Adding zinc salt, ferric salt, PVP and Pluronic F-127 into water, and uniformly stirring to obtain a yellow transparent solution A;
(2) Ultrasonically dissolving potassium cobalt cyanide in water to obtain a transparent solution B, and dripping the transparent solution B into the yellow transparent solution A under the condition of continuous stirring to form a yellow transparent solution C;
(3) Putting the transparent solution C obtained in the step (2) into an ice water bath for ultrasonic treatment to obtain a suspension C;
(4) Standing the suspension C obtained in the step (3), and then washing and drying the suspension C to obtain light yellow powder alpha, namely Yang Meizhuang FeZnCo-PBA precursor;
(5) Carrying out heat treatment on the light yellow powder alpha obtained in the step (4) under a protective atmosphere to obtain black powder beta, namely the iron/cobalt/carbon composite material;
(6) And (3) carrying out heat treatment on the black powder beta obtained in the step (5) and sulfur powder or selenium powder under the protection of inert gas to obtain black powder gamma, namely Yang Meizhuang iron-doped cobalt disulfide/nitrogen-doped carbon porous composite material or waxberry-shaped iron-doped cobalt diselenide/nitrogen-doped carbon porous composite material.
2. The method of claim 1, wherein: in the steps (1) and (2),
Fe 3+ and Zn 2+ The molar ratio of (1);
the mass ratio of PVP to Pluronic F-127 is 1.8;
the total molar ratio of the potassium cobalt cyanide to the metal ions is 4:5-2:3;
the mass ratio of the potassium cobalt cyanide to the PVP is 1:4-1.
3. The production method according to claim 1 or 2, characterized in that: in the step (1), the zinc salt is soluble zinc salt; the ferric salt is a trivalent ferric salt.
4. The method of claim 1, wherein:
in the step (1), the stirring time is 20-40 minutes;
in the step (2), the stirring time is 5-20 minutes.
5. The method of claim 1 or 2, wherein: in the step (3), ice-water bath ultrasound is carried out for 20-40 minutes at the temperature of 10-20 ℃.
6. The method of claim 1 or 2, wherein: in the step (4), the standing time is 6-48 hours, and the standing temperature is 15-30 ℃.
7. The method of claim 1 or 2, wherein: in the step (5), the step (c),
the heat treatment temperature is 600-1000 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time is 1-3 hours.
8. The method of claim 7, wherein: in the step (6), the step (c),
the mass ratio of the iron/cobalt/carbon composite material to the sulfur powder or selenium powder is 1:2-1:5;
the heat treatment temperature is 300-600 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time is 2-5 hours.
9. The method of claim 1 or 2, wherein:
in the step (5), the protective atmosphere of the heat treatment is nitrogen or argon;
in the step (6), the protective atmosphere is nitrogen or argon.
10. The application of the myrica-shaped iron-doped cobalt-based chalcogenide nitrogen-doped carbon porous composite material obtained by the preparation method according to claim 1 or 2 as a negative electrode material of a sodium-ion battery.
CN202211186912.3A 2022-09-26 2022-09-26 Preparation method and application of myrica-shaped iron-doped cobalt-based chalcogenide nitrogen-doped carbon porous composite material Pending CN115425209A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116332137A (en) * 2023-01-05 2023-06-27 南京信息工程大学 Multi-metal selenide wave-absorbing material and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116332137A (en) * 2023-01-05 2023-06-27 南京信息工程大学 Multi-metal selenide wave-absorbing material and preparation method thereof
CN116332137B (en) * 2023-01-05 2024-05-24 南京信息工程大学 Multi-metal selenide wave-absorbing material and preparation method thereof

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