CN112158800A - Porous V2O3-ZnTiO3rGO composite hydrogen storage material and preparation method thereof - Google Patents

Porous V2O3-ZnTiO3rGO composite hydrogen storage material and preparation method thereof Download PDF

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CN112158800A
CN112158800A CN202011090391.2A CN202011090391A CN112158800A CN 112158800 A CN112158800 A CN 112158800A CN 202011090391 A CN202011090391 A CN 202011090391A CN 112158800 A CN112158800 A CN 112158800A
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朱冬祥
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Abstract

The invention belongs to the field of hydrogen storage materials, and particularly relates to a porous V2O3‑ZnTiO3a/rGO composite hydrogen storage material and a preparation method thereof. The preparation method comprises the following steps: graphene oxide is prepared by a Hummers method, and ZnTiO is prepared by taking zinc acetate and tetrabutyl titanate as raw materials and performing reaction and calcination3(ii) a Then oxidizing the graphene oxide and the graphene oxide V2O3And ZnTiO3Reducing the mixture in a reaction kettle to obtain porous V2O3‑ZnTiO3a/rGO composite hydrogen storage material. Lithium of the inventionThe ion specific capacity is large, and the risk of volume expansion/contraction is avoided.

Description

Porous V2O3-ZnTiO3rGO composite hydrogen storage material and preparation method thereof
Technical Field
The invention belongs to the field of hydrogen storage materials, and particularly relates to a porous V2O3-ZnTiO3a/rGO composite hydrogen storage material and a preparation method thereof.
Background
The lithium ion battery has many advantages in the aspects of energy conversion and storage, and has the advantages of high energy density, reversible charging, no memory effect and environmental protection. Particularly, with the vigorous popularization of new energy automobiles in recent years, high-energy density lithium ion batteries are widely accepted as ideal power sources in electric automobiles and hybrid automobiles. And the lithium ion battery has light weight and long service life, so the lithium ion battery is also greatly applied to the field of portable electronic equipment such as notebook computers, intelligent watches, intelligent mobile phones, remote control equipment and the like.
The negative electrode is an important component of the lithium ion battery, plays a role in storing active lithium in the charge and discharge processes of the battery, and the energy density, the cycle life and the safety of the battery are determined by the negative electrode material; the change of the negative electrode material from pure metallic lithium to carbon material or other lithium-storing intercalation-type materials has led to the development of lithium batteries to lithium ion batteries. Most of the negative electrode materials of the existing commercial lithium ion batteries are graphite materials, and the negative electrode materials have the advantages of good conductivity, good cycling stability, low cost and the like. But the specific capacity of the graphite negative electrode material is only 372mAh/g, so that the energy density and the power density of the battery are determined to be lower; the graphite negative electrode material undergoes volume expansion/contraction during the lithium ion insertion/extraction process; and the graphite negative electrode material has low oxidation-reduction reaction potential and is easy to generate lithium dendrite so as to bring safety problem. Therefore, a negative electrode material with better hydrogen storage capacity is found.
Disclosure of Invention
Aiming at the technical defects that the graphite material of the cathode of the existing lithium ion battery has small hydrogen storage capacity and can expand/contract in volume, the invention provides a porous V2O3-ZnTiO3a/rGO composite hydrogen storage material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
porous V2O3-ZnTiO3The preparation method of the/rGO composite hydrogen storage material comprises the following steps:
step 1: preparing graphene oxide by using a Hummers method; sequentially adding a certain amount of potassium nitrate and graphite powder into a proper amount of concentrated sulfuric acid under an ice bath condition, stirring for 20-30min, slowly adding a proper amount of potassium permanganate into the solution, placing the solution at a water bath temperature of 35-38 ℃ after the addition is finished, quickly stirring for 2-3h, then slowly dropping a proper amount of deionized water into the mixed solution, and continuously stirring for 15-20min at a system temperature of 90-95 ℃; and then, dropwise adding a proper amount of hydrogen peroxide into the solution at room temperature until the solution is bright yellow, performing suction filtration, washing the solution for multiple times by using dilute hydrochloric acid, performing centrifugal washing by using deionized water until the washing solution is neutral, and then placing the sample in a vacuum oven at 50-60 ℃ for drying to obtain the graphene oxide.
Step 2: adding a proper amount of zinc acetate and tetrabutyl titanate into ethylene glycol, and carrying out ultrasonic treatment for 15-20min to obtain a mixed solution A; adding polyvinylpyrrolidone (PVP) into appropriate amount of ethylene glycol, performing ultrasonic treatment for 8-10min, slowly dripping concentrated ammonia water solution under stirring at room temperature, and continuously stirring for 50-60min to obtain mixed solution B; dropwise adding the mixed solution B into the mixed solution A, performing ultrasonic treatment for 10-15min after dropwise adding is completed, and placing the ultrasonic treated solution in a water bath at 50-55 ℃ to be violently stirred for 20-24 h; filtering to obtain a precursor after stirring, washing the precursor for 3 times by using absolute ethyl alcohol, and calcining in a muffle furnace at 650 ℃ for 3 hours to obtain ZnTiO with a one-dimensional rod-like porous structure3。
And step 3: adding an appropriate amount of graphene oxide prepared in the step 1 into deionized water, performing ultrasonic treatment for 5-8min, and then sequentially adding an appropriate amount of porous V into the graphene oxide2O3And ZnTiO prepared in step 23Continuing to perform ultrasonic treatment for 30-40min to obtain a mixed solution; then, a proper amount of hydrazine hydrate is dripped into the mixed solution, the mixed solution is placed in a reaction kettle at the temperature of 90-100 ℃ for reaction for 5-7 hours, the reaction kettle is cooled to room temperature and then filtered, and the filtered product is washed by absolute ethyl alcohol and deionized water for 3 times to obtain a porous V2O3-ZnTiO3a/rGO composite hydrogen storage material.
In the step 1, the mass ratio of potassium nitrate to graphite powder is 1:1.8-1:2, the mass ratio of graphite powder to potassium permanganate is 1:3.2-1:3.5, and the volume ratio of deionized water to concentrated sulfuric acid is 1.1:1-1.3: 1.
In the step 2, the mass ratio of the zinc acetate to the tetrabutyl titanate is 1:1.55-1:1.63, the mass ratio of the zinc acetate to the PVP is 1:0.73-1:0.85, and the dosage ratio of the zinc acetate to the concentrated ammonia water is 1g:0.48ml-1g:0.55 ml.
V in said step 32O3The mass ratio of the graphene oxide to the graphene oxide is 1:3.13-1:3.85, and ZnTiO is3And the mass ratio of the hydrazine hydrate to the graphene oxide is 1:1.69-1.85, and the volume ratio of the hydrazine hydrate to the graphene oxide solution is 1:20-1: 30.
Preferably, in the step 1, the concentration of the graphite powder in the concentrated sulfuric acid is 0.03g/ml, the dropping speeds of the deionized water and the hydrogen peroxide are both 3ml/min, and the concentration of the dilute hydrochloric acid is 4 mol/L.
Preferably, in the step 2, the concentration of the zinc acetate in the ethylene glycol is 0.03g/ml, the concentration of the PVP in the ethylene glycol is 0.06g/ml, the concentration of the concentrated ammonia solution is 28 wt%, the dropping speed of the concentrated ammonia solution is 2ml/min, and the heating rate of the muffle furnace is 8 ℃/min.
Preferably, the concentration of the graphene oxide solution in the step 3 is 3 mg/ml.
The invention also provides another technical scheme, and the porous V2O3-ZnTiO3/rGO composite hydrogen storage material prepared by the method, wherein V is2O3The loading on rGO is 26-32 wt%, ZnTiO3The loading on the loaded rGO was 54-59 wt%.
Another aspect of the present invention provides the above porous V2O3-ZnTiO3The composite material prepared by the preparation method of the/rGO composite hydrogen storage material is applied to a negative electrode material of a lithium ion battery.
Has the advantages that:
(1)V2O3and ZnTiO3The materials are nano-sized materials, and the load on the rGO ensures that the composite hydrogen storage material is easy to transfer mass and high in electron conductivity for charge transfer; avoid V2O3And ZnTiO3Can better exert V2O3And ZnTiO3The utilization rate of lithium storage sites of the material is improved under the actions of catalysis and the like in the electrolyte.
(2)ZnTiO3The composite material is of a one-dimensional rod-shaped porous structure, so that the diffusion efficiency of the electrolyte in the composite material can be improved, and the volume expansion/contraction in the lithium ion insertion/extraction process is relieved; the material provides more lithium storage space, and the lithium storage capacity is improved.
(3)V2O3The composite material has a porous structure, so that the specific surface area of the material can be increased in the composite material, the stress/strain generated during the insertion/extraction of lithium ions can be relieved, and the effective diffusion distance of the lithium ions can be reduced, thereby improving the capacity, the rate capability and the cycle performance. At the same time, V2O3For ZnTiO3And Li+The reaction of electrons has promoting effect, and ZnTiO is improved3The lithium storage efficiency of (a).
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
Step 1: preparing graphene oxide by using a Hummers method; sequentially adding potassium nitrate and graphite powder into concentrated sulfuric acid under an ice bath condition, stirring for 20min, slowly adding potassium permanganate into the solution, placing the solution at a water bath temperature of 35 ℃ after the addition is finished, quickly stirring for 2h, then slowly dropping deionized water into the mixed solution, and controlling the system temperature to be 90 ℃ and continuously stirring for 15 min; and then dripping hydrogen peroxide into the solution at room temperature until the solution is bright yellow, performing suction filtration, washing the solution for multiple times by using dilute hydrochloric acid, performing centrifugal washing by using deionized water until the washing solution is neutral, and then placing the sample in a vacuum oven at 50 ℃ for drying to obtain the graphene oxide. Wherein the dosage ratio of potassium nitrate to graphite powder is 1g:1.8g, the dosage ratio of graphite powder to potassium permanganate is 1g:3.5g, and the volume ratio of the deionized water to the concentrated sulfuric acid is 1.2: 1.
Step 2: adding zinc acetate and tetrabutyl titanate into ethylene glycol, and carrying out ultrasonic treatment for 15min to obtain a mixed solution A; adding PVP into ethylene glycol, performing ultrasonic treatment for 8min, slowly dropping concentrated ammonia water solution under the condition of stirring at room temperature, and continuously stirring for 50min after dropping to obtain a mixed solution B; dropwise adding the mixed solution B into the mixed solution A, performing ultrasonic treatment for 10min after the dropwise adding is completed, and placing the ultrasonic treated solution in a water bath at 50 ℃ to be vigorously stirred for 20 h; filtering to obtain a precursor after stirring, washing the precursor for 3 times by using absolute ethyl alcohol, and calcining in a muffle furnace at 650 ℃ for 3 hours to obtain ZnTiO with a one-dimensional rod-like porous structure3. Wherein the dosage ratio of the zinc acetate to the tetrabutyl titanate is 1g to 1.55g,the dosage ratio of the zinc acetate to the PVP is 1g:0.85g, and the dosage ratio of the zinc acetate to the stronger ammonia water is 1g:0.48 ml.
And step 3: adding the graphene oxide prepared in the step 1 into deionized water, performing ultrasonic treatment for 6min, and then sequentially adding porous V into the graphene oxide2O3And ZnTiO prepared in step 23Continuing to perform ultrasonic treatment for 30min to obtain a mixed solution; then adding hydrazine hydrate into the mixed solution dropwise, placing the mixed solution into a reaction kettle at the temperature of 90 ℃ for reaction for 6 hours, cooling the mixed solution to room temperature, filtering the mixed solution, and washing the filtered product for 3 times by using absolute ethyl alcohol and deionized water in sequence to obtain the porous V2O3-ZnTiO3a/rGO composite hydrogen storage material. Wherein V2O3The dosage ratio of the graphene oxide to the graphene oxide is 1g:3.13g, and ZnTiO is3And the dosage ratio of the graphene oxide is 1g to 1.69g, and the volume ratio of the hydrazine hydrate to the graphene oxide solution is 1 to 20.
Example 2
Step 1: preparing graphene oxide by using a Hummers method; sequentially adding potassium nitrate and graphite powder into concentrated sulfuric acid under an ice bath condition, stirring for 30min, slowly adding potassium permanganate into the solution, placing the solution at a water bath temperature of 36 ℃ after the addition is finished, quickly stirring for 2h, then slowly dropping deionized water into the mixed solution, and continuously stirring for 20min at a system temperature of 92 ℃; and then dripping hydrogen peroxide into the solution at room temperature until the solution is bright yellow, performing suction filtration, washing the solution for multiple times by using dilute hydrochloric acid, performing centrifugal washing by using deionized water until the washing solution is neutral, and then placing the sample in a vacuum oven at 60 ℃ for drying to obtain the graphene oxide. Wherein the dosage ratio of potassium nitrate to graphite powder is 1g:1.9g, the dosage ratio of graphite powder to potassium permanganate is 1g:3.4g, and the volume ratio of the deionized water to the concentrated sulfuric acid is 1.3: 1.
Step 2: adding zinc acetate and tetrabutyl titanate into ethylene glycol, and performing ultrasonic treatment for 20min to obtain a mixed solution A; adding PVP into ethylene glycol, performing ultrasonic treatment for 9min, slowly dropping concentrated ammonia water solution under the condition of stirring at room temperature, and continuously stirring for 60min after dropping to obtain a mixed solution B; dropwise adding the mixed solution B into the mixed solution A, performing ultrasonic treatment for 12min after the dropwise adding is completed, and placing the ultrasonic treated solution in a water bath at 51 ℃ to be violently stirred for 22 h; filtering after stirring to obtainWashing the precursor with absolute ethyl alcohol for 3 times, and calcining in a muffle furnace at 650 ℃ for 3h to obtain ZnTiO with a one-dimensional rod-like porous structure3. Wherein the dosage ratio of the zinc acetate to the tetrabutyl titanate is 1g:1.63g, the dosage ratio of the zinc acetate to the PVP is 1g:0.73g, and the dosage ratio of the zinc acetate to the stronger ammonia water is 1g:0.55 ml.
And step 3: adding the graphene oxide prepared in the step 1 into deionized water, performing ultrasonic treatment for 8min, and then sequentially adding porous V into the graphene oxide2O3And ZnTiO prepared in step 23Continuing to perform ultrasonic treatment for 35min to obtain a mixed solution; then adding hydrazine hydrate into the mixed solution dropwise, placing the mixed solution into a reaction kettle at 94 ℃ for reaction for 5 hours, cooling the mixed solution to room temperature, filtering the mixed solution, and washing the filtered product for 3 times by using absolute ethyl alcohol and deionized water to obtain porous V2O3-ZnTiO3a/rGO composite hydrogen storage material. Wherein V2O3The dosage ratio of the graphene oxide to the graphene oxide is 1g:3.85g, and ZnTiO is3And the dosage ratio of the graphene oxide is 1g to 1.85g, and the volume ratio of the hydrazine hydrate to the graphene oxide solution is 1 to 30.
Example 3
Step 1: preparing graphene oxide by using a Hummers method; sequentially adding potassium nitrate and graphite powder into concentrated sulfuric acid under an ice bath condition, stirring for 24min, slowly adding potassium permanganate into the solution, placing the solution in a water bath temperature of 37 ℃ after the addition is finished, quickly stirring for 3h, then slowly dropping deionized water into the mixed solution, and controlling the system temperature to be 95 ℃ and continuously stirring for 17 min; and then dripping hydrogen peroxide into the solution at room temperature until the solution is bright yellow, performing suction filtration, washing the solution for multiple times by using dilute hydrochloric acid, performing centrifugal washing by using deionized water until the washing solution is neutral, and then placing the sample in a vacuum oven at 57 ℃ for drying to obtain the graphene oxide. Wherein the dosage ratio of potassium nitrate to graphite powder is 1g:2g, the dosage ratio of graphite powder to potassium permanganate is 1g:3.3g, and the volume ratio of the deionized water to the concentrated sulfuric acid is 1.1: 1.
Step 2: adding zinc acetate and tetrabutyl titanate into ethylene glycol, and carrying out ultrasonic treatment for 17min to obtain a mixed solution A; adding PVP into ethylene glycol, performing ultrasonic treatment for 10min, slowly dropping concentrated ammonia water solution under stirring at room temperature, and droppingContinuing stirring for 57min after the reaction is finished to obtain a mixed solution B; dropwise adding the mixed solution B into the mixed solution A, performing ultrasonic treatment for 14min after the dropwise adding is completed, and placing the ultrasonic treated solution in a water bath at 54 ℃ for violently stirring for 23 h; filtering to obtain a precursor after stirring, washing the precursor for 3 times by using absolute ethyl alcohol, and calcining in a muffle furnace at 650 ℃ for 3 hours to obtain ZnTiO with a one-dimensional rod-like porous structure3. Wherein the dosage ratio of the zinc acetate to the tetrabutyl titanate is 1g:1.58g, the dosage ratio of the zinc acetate to the PVP is 1g:0.78g, and the dosage ratio of the zinc acetate to the stronger ammonia water is 1g:0.5 ml.
And step 3: adding the graphene oxide prepared in the step 1 into deionized water, performing ultrasonic treatment for 7min, and then sequentially adding porous V into the graphene oxide2O3And ZnTiO prepared in step 23Continuing to perform ultrasonic treatment for 40min to obtain a mixed solution; then, hydrazine hydrate is dripped into the mixed solution, the mixed solution is placed in a reaction kettle at the temperature of 98 ℃ for reaction for 7 hours, the reaction kettle is cooled to room temperature and then filtered, and the filtered product is washed by absolute ethyl alcohol and deionized water for 3 times to obtain porous V2O3-ZnTiO3a/rGO composite hydrogen storage material. Wherein V2O3The dosage ratio of the graphene oxide to the graphene oxide is 1g:3.6g, and ZnTiO is3And the dosage ratio of the graphene oxide is 1g to 1.78g, and the volume ratio of the hydrazine hydrate to the graphene oxide solution is 1 to 23.
Example 4
Step 1: preparing graphene oxide by using a Hummers method; sequentially adding potassium nitrate and graphite powder into concentrated sulfuric acid under an ice bath condition, stirring for 27min, slowly adding potassium permanganate into the solution, placing the solution at a water bath temperature of 38 ℃ after the addition is finished, quickly stirring for 3h, then slowly dropping deionized water into the mixed solution, and continuously stirring for 19min at a system temperature of 93 ℃; and then dripping hydrogen peroxide into the solution at room temperature until the solution is bright yellow, performing suction filtration, washing the solution for multiple times by using dilute hydrochloric acid, performing centrifugal washing by using deionized water until the washing solution is neutral, and then placing the sample in a vacuum oven at 53 ℃ for drying to obtain the graphene oxide. Wherein the dosage ratio of potassium nitrate to graphite powder is 1g:1.9g, the dosage ratio of graphite powder to potassium permanganate is 1g:3.2g, and the volume ratio of the deionized water to the concentrated sulfuric acid is 1.2: 1.
Step 2: adding zinc acetate and tetrabutyl titanate into ethylene glycol, and carrying out ultrasonic treatment for 19min to obtain a mixed solution A; adding PVP into ethylene glycol, performing ultrasonic treatment for 8min, slowly dropping concentrated ammonia water solution under the condition of stirring at room temperature, and continuously stirring for 53min after dropping to obtain a mixed solution B; dropwise adding the mixed solution B into the mixed solution A, performing ultrasonic treatment for 15min after the dropwise adding is completed, and placing the ultrasonic treated solution in a water bath at 55 ℃ to be vigorously stirred for 24 h; filtering to obtain a precursor after stirring, washing the precursor for 3 times by using absolute ethyl alcohol, and calcining in a muffle furnace at 650 ℃ for 3 hours to obtain ZnTiO with a one-dimensional rod-like porous structure3. Wherein the dosage ratio of the zinc acetate to the tetrabutyl titanate is 1g:1.61g, the dosage ratio of the zinc acetate to the PVP is 1g:0.82g, and the dosage ratio of the zinc acetate to the stronger ammonia water is 1g:0.52 ml.
And step 3: adding the graphene oxide prepared in the step 1 into deionized water, performing ultrasonic treatment for 5min, and then sequentially adding porous V into the graphene oxide2O3And ZnTiO prepared in step 23Continuing to perform ultrasonic treatment for 38min to obtain a mixed solution; then adding hydrazine hydrate into the mixed solution dropwise, placing the mixed solution into a reaction kettle at the temperature of 100 ℃ for reaction for 5 hours, cooling the mixed solution to room temperature, filtering the mixed solution, and washing the filtered product for 3 times by using absolute ethyl alcohol and deionized water in sequence to obtain the porous V2O3-ZnTiO3a/rGO composite hydrogen storage material. Wherein V2O3The dosage ratio of the graphene oxide to the graphene oxide is 1g:3.4g, and ZnTiO3And the dosage ratio of the graphene oxide is 1g to 1.73g, and the volume ratio of the hydrazine hydrate to the graphene oxide solution is 1 to 26.
Comparative example 1
The carbon fiber film lithium storage material compounded by carbon nano tubes and graphite sheets is taken as a comparative example 1.
The lithium storage materials prepared in examples 1-2 and comparative example 1 were made into a negative electrode plate of a battery, and assembled into a CR2032 type button lithium ion half-cell. And the charge-discharge cycle stability and specific discharge capacity of the electrode were tested at a current density of 0.1C by a blue-ray system, and the results are shown in table 1.
TABLE 1
Figure BDA0002721910490000071
As can be seen from Table 1, the specific capacities of examples 1-2 after 20 and 50 cycles are respectively over 680mAh/g and 625mAh/g, and the coulombic efficiencies are respectively about 98% and 97%; the specific capacity and coulombic efficiency of comparative example 1 were much lower than those of examples 1-2. This indicates that the lithium storage materials prepared in examples 1-2 have good lithium ion specific capacities. Moreover, the specific capacities of examples 1 and 2 after 100 cycles were 596.3mAh/g and 601.8mAh/g, and the specific capacity after 50 cycles was not much different, and the change of coulomb efficiency was not much; the specific capacity of comparative example 1 after 100 cycles was 315.3mAh/g, the droop was as high as 19.4%, and the coulombic efficiency was even lower than 74.2. Examples 1-2 thus show good cycling stability relative to comparative example 1.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention.

Claims (7)

1. Porous V2O3-ZnTiO3The preparation method of the/rGO composite hydrogen storage material is characterized by comprising the following steps:
step 1: preparing graphene oxide by using a Hummers method; sequentially adding a certain amount of potassium nitrate and graphite powder into concentrated sulfuric acid under an ice bath condition, stirring for 20-30min, slowly adding potassium permanganate into the solution, placing the solution at a water bath temperature of 35-38 ℃ after the addition is finished, quickly stirring for 2-3h, then slowly dropping deionized water into the mixed solution, and continuously stirring for 15-20min at a system temperature of 90-95 ℃; then dripping hydrogen peroxide into the solution at room temperature until the solution is bright yellow, then carrying out suction filtration, washing the solution for multiple times by using dilute hydrochloric acid, then centrifugally washing the solution by using deionized water until the washing solution is neutral, and then placing the sample in a vacuum oven at 50-60 ℃ for drying to obtain graphene oxide;
step 2: adding zinc acetate and tetrabutyl titanate into ethylene glycol, and performing ultrasonic treatment for 15-20min to obtainMixing the solution A; adding polyvinylpyrrolidone into ethylene glycol, performing ultrasonic treatment for 8-10min, slowly dropping concentrated ammonia water solution under stirring at room temperature, and continuously stirring for 50-60min to obtain mixed solution B; dropwise adding the mixed solution B into the mixed solution A, performing ultrasonic treatment for 10-15min after dropwise adding is completed, and placing the ultrasonic treated solution in a water bath at 50-55 ℃ to be violently stirred for 20-24 h; filtering to obtain a precursor after stirring, washing the precursor for 3 times by using absolute ethyl alcohol, and calcining in a muffle furnace at 650 ℃ for 3 hours to obtain ZnTiO with a one-dimensional rod-like porous structure3；
And step 3: adding the graphene oxide prepared in the step 1 into deionized water, performing ultrasonic treatment for 5-8min, and then sequentially adding porous V into the graphene oxide2O3And ZnTiO prepared in step 23Continuing to perform ultrasonic treatment for 30-40min to obtain a mixed solution; then adding hydrazine hydrate into the mixed solution dropwise, placing the mixed solution into a reaction kettle at the temperature of 90-100 ℃ for reaction for 5-7 hours, cooling the mixed solution to room temperature, filtering the mixed solution, and washing the filtered product with absolute ethyl alcohol and deionized water for 3 times to obtain the porous V2O3-ZnTiO3a/rGO composite hydrogen storage material.
2. A porous V according to claim 12O3-ZnTiO3The preparation method of the/rGO composite hydrogen storage material is characterized in that in the step 1, the mass ratio of potassium nitrate to graphite powder is 1:1.8-1:2, the mass ratio of graphite powder to potassium permanganate is 1:3.2-1:3.5, and the volume ratio of deionized water to concentrated sulfuric acid is 1.1:1-1.3: 1; the concentration of graphite powder in concentrated sulfuric acid is 0.03g/ml, the dropping speeds of deionized water and hydrogen peroxide are both 3ml/min, and the concentration of dilute hydrochloric acid is 4 mol/L.
3. A porous V according to claim 12O3-ZnTiO3The preparation method of the/rGO composite hydrogen storage material is characterized in that in the step 2, the mass ratio of zinc acetate to tetrabutyl titanate is 1:1.55-1:1.63, the mass ratio of zinc acetate to polyvinylpyrrolidone is 1:0.73-1:0.85, and the dosage ratio of zinc acetate to concentrated ammonia water is 1g:0.48ml-1g:0.55 ml.
4. A porous V according to claim 12O3-ZnTiO3The preparation method of the/rGO composite hydrogen storage material is characterized in that in the step 2, the concentration of zinc acetate in glycol is 0.03g/ml, the concentration of polyvinylpyrrolidone in glycol is 0.06g/ml, the concentration of concentrated ammonia water solution is 28 wt%, the dropping speed of the concentrated ammonia water solution is 2ml/min, and the heating rate of a muffle furnace is 8 ℃/min.
5. A porous V according to claim 12O3-ZnTiO3The preparation method of the/rGO composite hydrogen storage material is characterized in that V in the step 32O3The mass ratio of the graphene oxide to the graphene oxide is 1:3.13-1:3.85, and ZnTiO is3The mass ratio of the hydrazine hydrate to the graphene oxide is 1:1.69-1.85, and the volume ratio of the hydrazine hydrate to the graphene oxide solution is 1:20-1: 30; the concentration of the graphene oxide solution was 3 mg/ml.
6. A porous V according to any one of claims 1 to 52O3-ZnTiO3The preparation method of the/rGO composite hydrogen storage material is characterized in that V in the lithium storage material2O3The loading on rGO is 26-32 wt%, ZnTiO3The loading on the loaded rGO was 54-59 wt%.
7. A porous V according to any one of claims 1 to 62O3-ZnTiO3The composite material prepared by the preparation method of the/rGO composite hydrogen storage material is applied to the negative electrode of a lithium ion battery.
CN202011090391.2A 2020-10-13 2020-10-13 Porous V2O3-ZnTiO3rGO composite hydrogen storage material and preparation method thereof Withdrawn CN112158800A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114132957A (en) * 2021-11-29 2022-03-04 东北大学秦皇岛分校 Preparation method of two-phase zinc metatitanate negative electrode material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114132957A (en) * 2021-11-29 2022-03-04 东北大学秦皇岛分校 Preparation method of two-phase zinc metatitanate negative electrode material
CN114132957B (en) * 2021-11-29 2023-09-29 东北大学秦皇岛分校 Preparation method of biphase zinc metatitanate negative electrode material

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