CN108832100B - Preparation method of carbon-coated zinc ferrite/graphene composite negative electrode material - Google Patents
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Abstract
The invention relates to a preparation method of a carbon-coated zinc ferrite/graphene composite negative electrode material. Preparing a carbon particle template by using sugar as a raw material through a hydrothermal method; adding zinc salt and ferric salt into carbon particles serving as a template, preparing a zinc ferrite precursor by taking alkali as a precipitator, and obtaining zinc ferrite nanoparticles by precursor pyrolysis in an air atmosphere; and respectively adding anionic polyelectrolyte and graphene oxide in two steps, and sintering in a nitrogen atmosphere to obtain the target carbon-coated zinc ferrite/graphene composite negative electrode material. The method is simple to operate, is easy for batch production, and uses water or ethanol solvent which is environment-friendly. The size of zinc ferrite in the composite negative electrode material obtained by the method is about 20 nanometers, the thin 2-nanometer carbon layer is uniformly coated on the outer layer of the zinc ferrite nano particles, the carbon layer and the zinc ferrite have strong covalent bond effect, and the graphene and the carbon layer form a double carbon coating structure, so that the composite negative electrode material forms a three-dimensional conductive network, and the composite material has excellent rate capability and cycle performance.
Description
Technical Field
The invention belongs to the technical field of electrode materials and application thereof, and particularly relates to a preparation method of a carbon-coated zinc ferrite/graphene composite negative electrode material.
Background
Lithium ion batteries are widely used in various portable electronic products due to their advantages of high energy density, high operating voltage, long service life, environmental friendliness, and no memory effect. However, with the rapid development of electric vehicles and large-scale energy storage devices, higher requirements are placed on the capacity, energy density and rapid charging and discharging capability of lithium ion batteries. The development of high-performance electrode materials is a key factor for improving the performance of lithium ion batteries. Most of the current commercialized lithium ion battery negative electrode materials use graphite carbon materials, but lithium dendrite is easy to generate in the charging and discharging process, the hidden danger of battery explosion exists, the theoretical specific capacity is low (372 mAh/g), and the requirement of a new generation of high-capacity energy storage equipment is difficult to meet. Therefore, the search for high-capacity, long-cycle-life and high-safety cathode materials has become the focus of research on lithium ion batteries.
The transition metal oxide has a high theoretical specific capacity (500-1000 mAh/g), so that the transition metal oxide attracts wide attention. Among them, zinc ferrite has higher theoretical capacity (1000.5 mAh/g) and lower lithium-intercalation-deintercalation platform than common transition metal oxide, and has rich raw material sources, no toxicity, environmental protection and safety, thus being favored. However, zinc ferrite has the defects of poor conductivity, large volume change of the material in the charging and discharging processes and easy agglomeration, so that the cycle performance and rate capability of the material are greatly reduced.
Aiming at the problem, the performance of the zinc ferrite negative electrode material is improved mainly by nanocrystallizing the material and compounding the material with a carbon material at present. However, the current zinc ferrite-carbon composite negative electrode material has the main defects that: (1) the zinc ferrite has magnetism and is easy to agglomerate in the preparation process, so that the obtained composite material is not uniform; (2) the zinc ferrite and the carbon material have different volume expansion rates in the charging and discharging processes, so that the zinc ferrite and the carbon material are easy to separate; (3) the interface performance of zinc ferrite and carbon materials is poor.
Disclosure of Invention
Aiming at the defects of a pure-phase zinc ferrite negative electrode material, firstly preparing nano-scale zinc ferrite, taking an anionic polyelectrolyte of a polyacid as a carbon source to enable the zinc ferrite and carbon to generate strong covalent bond action, and then introducing graphene to form a three-dimensional conductive network structure, so that the carbon-coated zinc ferrite/graphene composite negative electrode material is prepared, and the problems of poor conductivity, poor cycle performance and poor rate capability of the electrode material are solved.
The invention provides a preparation method of a carbon-coated zinc ferrite/graphene composite negative electrode material, which comprises the following specific steps:
(1) dissolving sugar in deionized water to obtain a sugar solution with the concentration of 0.2-2 mol/L, then placing the sugar solution in a hydrothermal kettle, heating at 140-200 ℃ for 2-10 hours, centrifuging the reactant, alternately washing for 4 times by using ethanol and deionized water, and drying to obtain carbon particle powder;
(2) adding the carbon particle powder obtained in the step (1) into an ethanol solution, performing ultrasonic dispersion, and stirring to obtain a carbon particle-ethanol dispersion liquid; dissolving zinc salt and iron salt in ethanol, dropwise adding the solution into the carbon particle-ethanol dispersion solution, and magnetically stirring the solution for 0.1 to 10 hours to obtain a first mixed dispersion solution; slowly dropwise adding an alkaline ethanol solution into the first mixed dispersion liquid, magnetically stirring for 2 hours, centrifuging, washing with water, and freeze-drying to obtain powder; then placing the obtained powder in a tube furnace, calcining for 0.5-5 hours at 800 ℃ in an air atmosphere of 200-: the molar ratio of zinc to iron in the zinc salt and the iron salt is 1.5:2, and the molar ratio of the zinc salt to alkali is 1.5: 9;
(3) ultrasonically dispersing the zinc ferrite powder obtained in the step (2) in deionized water, adding anionic polyelectrolyte, and magnetically stirring for 0.1-10 hours to obtain a mixed dispersion of the zinc ferrite and the anionic polyelectrolyte; then ultrasonically dispersing graphite oxide powder into deionized water to obtain a graphene oxide aqueous dispersion; adding the graphene oxide aqueous dispersion into a mixed dispersion of zinc ferrite and anionic polyelectrolyte, and continuously magnetically stirring for 0.1-10 hours to obtain a second mixed dispersion; placing a sample obtained after the obtained second mixed dispersion liquid is subjected to freeze drying in a tubular furnace, and calcining for 0.5-5 hours at 800 ℃ in a nitrogen atmosphere to obtain a carbon-coated zinc ferrite/graphene composite negative electrode material; the mass ratio of the zinc ferrite to the anionic polyelectrolyte is 1: (0.1-2); the mass ratio of the zinc ferrite to the graphite oxide is 1: (0.1-2).
In the present invention, the sugar in step (1) is any one of glucose, fructose and sucrose.
In the invention, the zinc salt in the step (2) is any one of zinc chloride, zinc nitrate, zinc sulfate, zinc acetate or corresponding crystalline hydrate.
In the invention, the ferric salt in the step (2) is any one of ferric chloride, ferric nitrate, ferric sulfate, ferric acetate or corresponding crystalline hydrate.
In the present invention, the ratio of the carbon particles to the zinc salt in the step (2) is (50-500 mg): 1 millimole.
In the invention, the alkali in the step (2) is any one of sodium hydroxide, potassium hydroxide or ammonia water.
In the invention, the anionic polyelectrolyte in the step (3) is a polyacid polyelectrolyte, specifically any one of polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid or polyvinyl phosphoric acid.
The invention has the advantages that: firstly, zinc ferrite nano-particles with uniform size are obtained by means of a carbon particle template, the size of the zinc ferrite nano-particles is about 20 nanometers, secondly, the high-affinity polyacid type anion polyelectrolyte is used as a carbon source, so that the zinc ferrite and the carbon source have a strong effect, the agglomeration of the zinc ferrite in the carbon coating process is reduced, and a uniform carbon-coated zinc ferrite composite material is obtained, thirdly, graphene is introduced into the carbon-coated zinc ferrite composite material to form a three-dimensional conductive network structure, so that the problem of poor conductivity of an electrode material is solved, moreover, after high-temperature carbonization, the zinc ferrite and carbon have a strong covalent bond effect, so that the composite material is not separated in the charging and discharging process, and the obtained carbon-coated zinc ferrite/graphene composite negative electrode material has excellent cycle performance (the specific discharge capacity is up to 942 mAh/g after 500 times of cyclic charging and discharging under the current density of 0.2A/g) and rate performance (the specific discharge capacity under the current density of 5A/g is 0.1 67.8% of the specific discharge capacity at A/g current density). The scheme is simple to operate and easy for batch production, solves the key problems of poor cycle life and rate performance of zinc ferrite, and provides an effective way for realizing the application of the zinc ferrite material in the cathode of the lithium ion battery.
Drawings
Fig. 1 is an X-ray diffraction spectrum of a carbon-coated zinc ferrite/graphene composite negative electrode material.
FIG. 2 is a field emission scanning electron micrograph of zinc ferrite.
FIG. 3 is a transmission electron micrograph of carbon-coated zinc ferrite.
FIG. 4 is a field emission scanning electron microscope photograph of the carbon-coated zinc ferrite/graphene composite negative electrode material.
Fig. 5 is a rate performance diagram of the carbon-coated zinc ferrite/graphene composite negative electrode material.
FIG. 6 is a cycle performance diagram of the carbon-coated zinc ferrite/graphene composite negative electrode material at 0.2A/g.
Detailed Description
The following further describes a specific embodiment of a method for preparing a carbon-coated zinc ferrite/graphene composite anode material according to the present invention with reference to the drawings, and examples are provided to facilitate understanding of the present invention, but the present invention is by no means limited thereto, and the present invention is not limited to the following embodiments. Other insubstantial changes from the above disclosure are intended to be covered by the present invention.
Example 1
(1) Dissolving glucose in deionized water to obtain a glucose solution with the concentration of 0.5 mol/L, then placing the glucose solution in a hydrothermal kettle, heating for 8 hours at 180 ℃, centrifuging the reactant, alternately washing for 4 times by using ethanol and deionized water, and drying to obtain carbon particle powder;
(2) adding the carbon particle powder (150 mg) obtained in the step (1) into an ethanol solution, performing ultrasonic dispersion, and stirring to obtain a carbon particle-ethanol dispersion liquid; dissolving zinc chloride (1.5 mmol) and ferric chloride hexahydrate (2 mmol) in ethanol, dropwise adding the solution into the carbon particle-ethanol dispersion solution, and magnetically stirring for 5 hours to obtain a first mixed dispersion solution; slowly dropwise adding an ethanol solution of ammonia water (9 millimoles) into the first mixed dispersion liquid, magnetically stirring for 2 hours, centrifuging, washing with water, and freeze-drying to obtain powder; then putting the obtained powder into a tubular furnace, calcining for 2 hours at the air atmosphere of 500 ℃ to obtain zinc ferrite powder; (3) ultrasonically dispersing the zinc ferrite powder (100 mg) obtained in the step (2) in deionized water, adding polyacrylic acid (50 mg), and magnetically stirring for 5 hours to obtain a mixed dispersion liquid of the zinc ferrite and the polyacrylic acid; then, ultrasonically dispersing graphite oxide powder (20 mg) into deionized water to obtain a graphene oxide aqueous dispersion; adding the graphene oxide aqueous dispersion into a mixed dispersion of zinc ferrite and polyacrylic acid, and continuing to magnetically stir for 5 hours to obtain a second mixed dispersion; and placing a sample obtained after the obtained second mixed dispersion liquid is subjected to freeze drying in a tubular furnace, and calcining for 2 hours at 500 ℃ in a nitrogen atmosphere to obtain the carbon-coated zinc ferrite/graphene composite negative electrode material.
The zinc ferrite in the obtained carbon-coated zinc ferrite/graphene composite negative electrode material can be seen as a spinel structure through X-ray diffraction (figure 1). The field emission scanning electron micrograph shows that the preparation method successfully obtains uniform zinc ferrite nano particles with the diameter of about 20 nanometers (figure 2). FIG. 3 shows that 2 nm carbon layer is uniformly coated on the surface of zinc ferrite. Fig. 4 shows that carbon-coated zinc ferrite nanoparticles are coated with a thin layer of graphene. From the rate performance graph, it can be known that the specific discharge capacity of the carbon-coated zinc ferrite/graphene composite negative electrode material under the current density of 5A/g is 67.8% of the specific discharge capacity under the current density of 0.1A/g (fig. 5). FIG. 6 shows a cycle performance diagram, in which the specific discharge capacity of the carbon-coated zinc ferrite/graphene composite negative electrode material reaches 942 mAh/g after being charged and discharged for 500 times under 0.2A/g, which is 99.2% of the specific discharge capacity of the second time.
Example 2
(1) Dissolving fructose in deionized water to obtain a fructose solution with the concentration of 1 mol/L, then placing the fructose solution in a hydrothermal kettle, heating for 8 hours at 160 ℃, centrifuging the reactant, alternately washing for 4 times by using ethanol and deionized water, and drying to obtain carbon particle powder;
(2) adding the carbon particle powder (200 mg) obtained in the step (1) into an ethanol solution, performing ultrasonic dispersion, and stirring to obtain a carbon particle-ethanol dispersion liquid; dissolving zinc nitrate hexahydrate (1.5 mmol) and ferric nitrate nonahydrate (2 mmol) in ethanol, dropwise adding the solution into the carbon particle-ethanol dispersion, and magnetically stirring for 0.1 hour to obtain a first mixed dispersion; slowly dropwise adding an ethanol solution of sodium hydroxide (9 millimoles) into the first mixed dispersion liquid, magnetically stirring for 2 hours, centrifuging, washing with water, and freeze-drying to obtain powder; then putting the obtained powder into a tubular furnace, calcining for 0.5 hour at 800 ℃ in air atmosphere to obtain zinc ferrite powder;
(3) ultrasonically dispersing the zinc ferrite powder (100 mg) obtained in the step (2) in deionized water, adding polymethacrylic acid (150 mg), and magnetically stirring for 10 hours to obtain a mixed dispersion of the zinc ferrite and the polymethacrylic acid; then, ultrasonically dispersing graphite oxide powder (10 mg) into deionized water to obtain a graphene oxide aqueous dispersion; adding the graphene oxide aqueous dispersion into a mixed dispersion of zinc ferrite and polymethacrylic acid, and continuing to magnetically stir for 0.1 hour to obtain a second mixed dispersion; and placing a sample obtained after the obtained second mixed dispersion liquid is subjected to freeze drying in a tubular furnace, and calcining for 0.5 hour at 500 ℃ in a nitrogen atmosphere to obtain the carbon-coated zinc ferrite/graphene composite negative electrode material.
Example 3
(1) Dissolving sucrose in deionized water to obtain a sucrose solution with the concentration of 0.2 mol/L, then placing the sucrose solution in a hydrothermal kettle, heating for 2 hours at 180 ℃, centrifuging the reactant, alternately washing for 4 times by using ethanol and deionized water, and drying to obtain carbon particle powder;
(2) adding the carbon particle powder (250 mg) obtained in the step (1) into an ethanol solution, performing ultrasonic dispersion, and stirring to obtain a carbon particle-ethanol dispersion liquid; dissolving zinc sulfate heptahydrate (1.5 mmol) and ferric sulfate (1 mmol) in ethanol, dropwise adding into the carbon particle-ethanol dispersion, and magnetically stirring for 10 hours to obtain a first mixed dispersion; slowly dropwise adding an ethanol solution of ammonia water (9 millimoles) into the first mixed dispersion liquid, magnetically stirring for 2 hours, centrifuging, washing with water, and freeze-drying to obtain powder; then placing the obtained powder in a tubular furnace, calcining for 5 hours at the temperature of 400 ℃ in air atmosphere to obtain zinc ferrite powder;
(3) ultrasonically dispersing the zinc ferrite powder (100 mg) obtained in the step (2) in deionized water, adding polystyrene sulfonic acid (10 mg), and magnetically stirring for 0.1 hour to obtain a mixed dispersion liquid of the zinc ferrite and the polystyrene sulfonic acid; then, ultrasonically dispersing graphite oxide powder (200 mg) into deionized water to obtain a graphene oxide aqueous dispersion; adding the graphene oxide aqueous dispersion into a mixed dispersion of zinc ferrite and polystyrene sulfonic acid, and continuing to magnetically stir for 5 hours to obtain a second mixed dispersion; and placing a sample obtained after the obtained second mixed dispersion liquid is subjected to freeze drying in a tubular furnace, and calcining for 5 hours at 800 ℃ in a nitrogen atmosphere to obtain the carbon-coated zinc ferrite/graphene composite negative electrode material.
Example 4
(1) Dissolving glucose in deionized water to obtain a glucose solution with the concentration of 2 mol/L, then placing the glucose solution in a hydrothermal kettle, heating for 8 hours at 140 ℃, centrifuging the reactant, alternately washing for 4 times by using ethanol and deionized water, and drying to obtain carbon particle powder;
(2) adding the carbon particle powder (75 mg) obtained in the step (1) into an ethanol solution, performing ultrasonic dispersion, and stirring to obtain a carbon particle-ethanol dispersion liquid; dissolving zinc chloride (1.5 mmol) and ferric chloride hexahydrate (2 mmol) in ethanol, dropwise adding the solution into the carbon particle-ethanol dispersion solution, and magnetically stirring for 8 hours to obtain a first mixed dispersion solution; slowly dropwise adding an ethanol solution of potassium hydroxide (9 millimoles) into the first mixed dispersion liquid, magnetically stirring for 2 hours, centrifuging, washing with water, and freeze-drying to obtain powder; then putting the obtained powder into a tubular furnace, calcining for 3 hours at the air atmosphere of 200 ℃ to obtain zinc ferrite powder;
(3) ultrasonically dispersing the zinc ferrite powder (100 mg) obtained in the step (2) in deionized water, adding polyacrylic acid (50 mg), and magnetically stirring for 5 hours to obtain a mixed dispersion liquid of the zinc ferrite and the polyacrylic acid; then, ultrasonically dispersing graphite oxide powder (100 mg) into deionized water to obtain a graphene oxide aqueous dispersion; adding the graphene oxide aqueous dispersion into a mixed dispersion of zinc ferrite and polyacrylic acid, and continuing to magnetically stir for 10 hours to obtain a second mixed dispersion; and placing a sample obtained after the obtained second mixed dispersion liquid is subjected to freeze drying in a tubular furnace, and calcining for 3 hours at 200 ℃ in a nitrogen atmosphere to obtain the carbon-coated zinc ferrite/graphene composite negative electrode material.
Example 5
(1) Dissolving glucose in deionized water to obtain a glucose solution with the concentration of 0.5 mol/L, then placing the glucose solution in a hydrothermal kettle, heating for 10 hours at 200 ℃, centrifuging the reactant, alternately washing for 4 times by using ethanol and deionized water, and drying to obtain carbon particle powder;
(2) adding the carbon particle powder (750 mg) obtained in the step (1) into an ethanol solution, performing ultrasonic dispersion, and stirring to obtain a carbon particle-ethanol dispersion liquid; dissolving zinc chloride (1.5 mmol) and ferric chloride hexahydrate (2 mmol) in ethanol, dropwise adding the solution into the carbon particle-ethanol dispersion solution, and magnetically stirring for 5 hours to obtain a first mixed dispersion solution; slowly dropwise adding an ethanol solution of sodium hydroxide (9 millimoles) into the first mixed dispersion liquid, magnetically stirring for 2 hours, centrifuging, washing with water, and freeze-drying to obtain powder; then placing the obtained powder in a tubular furnace, calcining for 1 hour at 600 ℃ in air atmosphere to obtain zinc ferrite powder;
(3) ultrasonically dispersing the zinc ferrite powder (100 mg) obtained in the step (2) in deionized water, adding polyethylene phosphoric acid (50 mg), and magnetically stirring for 5 hours to obtain a mixed dispersion of the zinc ferrite and the polyethylene phosphoric acid; then, ultrasonically dispersing graphite oxide powder (50 mg) into deionized water to obtain a graphene oxide aqueous dispersion; adding the graphene oxide aqueous dispersion into a mixed dispersion of zinc ferrite and polyethylene phosphate, and continuing to magnetically stir for 8 hours to obtain a second mixed dispersion; and placing a sample obtained after the obtained second mixed dispersion liquid is subjected to freeze drying in a tubular furnace, and calcining for 4 hours at the temperature of 400 ℃ in a nitrogen atmosphere to obtain the carbon-coated zinc ferrite/graphene composite negative electrode material.
Claims (5)
1. A preparation method of a carbon-coated zinc ferrite/graphene composite negative electrode material is characterized by comprising the following specific steps:
(1) dissolving sugar in deionized water to obtain a sugar solution with the concentration of 0.2-2 mol/L, then placing the sugar solution in a hydrothermal kettle, heating at 140-200 ℃ for 2-10 hours, centrifuging the reactant, alternately washing for 4 times by using ethanol and deionized water, and drying to obtain carbon particle powder;
(2) adding the carbon particle powder obtained in the step (1) into an ethanol solution, performing ultrasonic dispersion, and stirring to obtain a carbon particle-ethanol dispersion liquid; dissolving zinc salt and iron salt in ethanol, dropwise adding the solution into the carbon particle-ethanol dispersion solution, and magnetically stirring the solution for 0.1 to 10 hours to obtain a first mixed dispersion solution; slowly dropwise adding an alkaline ethanol solution into the first mixed dispersion liquid, magnetically stirring for 2 hours, centrifuging, washing with water, and freeze-drying to obtain powder; then placing the obtained powder in a tube furnace, calcining for 0.5-5 hours at 800 ℃ in an air atmosphere of 200-: the molar ratio of zinc to iron in the zinc salt and the iron salt is 1.5:2, and the molar ratio of the zinc salt to alkali is 1.5: 9; the ratio of carbon particles to zinc salt is (50-500 mg): 1 millimole;
(3) ultrasonically dispersing the zinc ferrite powder obtained in the step (2) in deionized water, adding anionic polyelectrolyte, and magnetically stirring for 0.1-10 hours to obtain a mixed dispersion of the zinc ferrite and the anionic polyelectrolyte; then ultrasonically dispersing graphite oxide powder into deionized water to obtain a graphene oxide aqueous dispersion; adding the graphene oxide aqueous dispersion into a mixed dispersion of zinc ferrite and anionic polyelectrolyte, and continuously magnetically stirring for 0.1-10 hours to obtain a second mixed dispersion; placing a sample obtained after the obtained second mixed dispersion liquid is subjected to freeze drying in a tubular furnace, and calcining for 0.5-5 hours at 800 ℃ in a nitrogen atmosphere to obtain a carbon-coated zinc ferrite/graphene composite negative electrode material; the mass ratio of the zinc ferrite to the anionic polyelectrolyte is 1: (0.1-2); the mass ratio of the zinc ferrite to the graphite oxide is 1: (0.1-2); the anionic polyelectrolyte is a polyacid polyelectrolyte, specifically any one of polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid or polyvinyl phosphoric acid.
2. The method for preparing the carbon-coated zinc ferrite/graphene composite anode material according to claim 1, wherein the sugar in the step (1) is any one of glucose, fructose and sucrose.
3. The preparation method of the carbon-coated zinc ferrite/graphene composite negative electrode material according to claim 1, wherein the zinc salt in the step (2) is any one of zinc chloride, zinc nitrate, zinc sulfate, zinc acetate or corresponding crystalline hydrate.
4. The preparation method of the carbon-coated zinc ferrite/graphene composite anode material according to claim 1, wherein the iron salt in the step (2) is any one of ferric chloride, ferric nitrate, ferric sulfate, ferric acetate or corresponding crystalline hydrate.
5. The method for preparing the carbon-coated zinc ferrite/graphene composite anode material according to claim 1, wherein the alkali in the step (2) is any one of sodium hydroxide, potassium hydroxide or ammonia water.
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