CN105895869A - Preparation method of nickel sulfide/graphene/cobalt sulfide three-dimensional composite hydrogen storage material - Google Patents
Preparation method of nickel sulfide/graphene/cobalt sulfide three-dimensional composite hydrogen storage material Download PDFInfo
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Abstract
The invention provides a preparation method of a nickel sulfide/graphene/cobalt sulfide three-dimensional composite hydrogen storage material, relates to a method for preparing the three-dimensional composite hydrogen storage material and aims at solving the technical problem that an existing cobalt sulfide composite material cannot be used as an electrochemical hydrogen storage electrode. The method comprises the following steps: (1) preparing a graphene oxide disperse solution; (2) adding cobaltous acetate and sulphur to the graphene oxide disperse solution to prepare a mixed solution; (3) preparing a mixed dispersion liquid in a ball-milling manner; (4) cleaning nickel foam; and (5) adding the mixed dispersion liquid to a hydrothermal kettle, adding glucose, immersing the nickel foam into the mixed dispersion liquid, carrying out hydrothermal reaction and then carrying out cleaning and freeze drying on the product to obtain the nickel sulfide/graphene/cobalt sulfide three-dimensional composite hydrogen storage material. The specific surface area of the composite hydrogen storage material is 67-78m<2>/g; the preparation method is simple; the reaction period is short; final treatment is not needed; the hydrogen storage property is high; and the nickel sulfide/graphene/cobalt sulfide three-dimensional composite hydrogen storage material can be directly applied to the field of electrochemical hydrogen storage as the hydrogen storage electrode.
Description
Technical field
The method that the present invention relates to three-dimensional composite hydrogen storage material, particularly to the preparation side of a kind of electrochemical hydrogen storage electrode material
Method.
Background technology
Energy crisis and environmental pollution have become as a global difficult problem, in order to realize the sustainable development of society, countries in the world
Continue to increase the exploitation of new forms of energy, to obtaining the free of contamination energy of high-efficiency cleaning.In new forms of energy, Hydrogen Energy is because having the highest energy
Matter ratio, the advantage such as cleanliness without any pollution during use, its development and utilization has obtained paying close attention to widely.But Hydrogen Energy is difficult to storage,
Through long-term research, scientific research personnel finds that solid hydrides can realize the reversible utilization of Hydrogen Energy by electrochemical means, then store up
The research emphasis of hydrogen technology has turned to the exploitation of solid hydrogen storage material.
In recent years, the metal nickel sulfide of various nanostructureds and cobalt sulfide are found to have good electrochemical hydrogen storage prospect, but
The powder body hydrogen storage material obtained needs to add the auxiliary material such as conductive agent, binding agent in preparing electrode process and repastes and be overlying on afflux
On body, make electrode production process take time and effort and add the contact resistance of electrode, causing high magnification hydrogen storage property to be deteriorated,
Additionally, conductive agent, binding agent and current collector itself can increase the gross mass of electrode so that electrode entirety specific capacity reduces many.
Therefore, find a kind of composite hydrogen-storing electrode material having high power capacity and good stability concurrently and become the key of development.
In prior art, the Chinese patent of Application No. 201310438808 discloses a kind of nickel foam nanometer eight sulfuration
Nine cobalt composite materials and preparation method thereof, utilize cobalt salt and carbamide to directly obtain a kind of Ni-based eight sulfuration nine cobalts by ionic reaction
Nano-tube array electrode material for super capacitor, but in this kind of material eight sulfuration nine cobalts be two kinds of solvable predecessors by fully from
The nano-tube array that son reaction obtains, if directly applying it as electrochemical hydrogen bearing material, its hydrogen storage property is relatively low.Application number
Be 201510307149.9 Chinese patent disclose one and prepare metal sulfide/Graphene/nickel sulfide composite film material
Method, sulfur source is still solvable thiourea or sodium sulfide, and the product finally given is thin film, and specific surface area is less, the most not
It is suitable for being directly applied to electrochemical hydrogen storage field.
In order to obtain the most excellent stable 3-D solid structure of combination property and there is the electrochemical hydrogen storage in high activity site
Material, to meet the application requirement that it is improved by new technique and frontier day by day, is just becoming association area and is needing the technology of solution badly
Problem.
Summary of the invention
The present invention is to solve that existing cobalt sulfide composite cannot act as the technical problem of electrochemical hydrogen storage electrode, and provide
A kind of preparation method of nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material.
The preparation method of a kind of nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material of the present invention sequentially includes the following steps:
One, preparing graphene oxide dispersion soln by Hummers method, regulation concentration is 1.8-2.2mg/ml；
Two, by cobalt acetate and sulfur with mol ratio as 1:(3～4) join in graphene oxide dispersion soln, continue stirring until all
Even, obtain mixed liquor；Wherein cobalt acetate is 1:(0.2～0.5 with the mass ratio of Graphene)；
Three, by ZrO2The mass ratio of abrading-ball and mixed liquor is 1:(15～20) ratio, by ZrO2Abrading-ball loads tool with mixed liquor
There is ZrO2In the ball grinder of liner, it is filled with high-purity argon gas, finally ball grinder is fixed in ball mill, at drum's speed of rotation be
Ball milling 4～8h under conditions of 500～700rpm, treat that ball milling terminates, and after ball grinder is cooled to room temperature, obtain mixed dispersion liquid；
Four, be 1:(2～4 by the ratio of width and water heating kettle diameter) nickel foam successively at deionization acetone, ethanol and deionization
Ultrasonic cleaning in water, after nickel foam being dried up with high-purity argon gas, then cleans 15～30 minutes with plasma washing machine；
Five, the mixed dispersion liquid that step 3 prepares is joined in water heating kettle, then press the mass ratio of glucose and mixed dispersion liquid
For 1:(100～120) add glucose, and the nickel foam after step 4 processes is immersed in mixed dispersion liquid,
180 DEG C～during 220 DEG C of Water Under thermal response 18～24；After reaction terminates, product is used deionized water drip washing, lyophilization 24～48
Hour, obtain nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material.
The present invention utilizes hydro-thermal method to prepare nickel sulfide/Graphene/cobalt sulfide three-dimensional with indissoluble thing elemental sulfur as sulfur source and is combined
Hydrogen storage material, owing to elemental sulfur dissolubility in aqueous is extremely low, through mechanical milling process activate after, can in water-heat process with nickel
Source, cobalt source slowly react, generating structure hydrogen storage more uniform, high activity unformed sulfide and be attached to Graphene
On activation site, in water-heat process, surfactant glucose is oxidized to pentose, glucuronic acid and glucoside etc. and spreads out
Biology, because glucose molecule and derivant thereof have abundant hydroxyl and carboxyl, so a part of glucose molecule and derivative
Thing can form stable chelate with cobalt ion and nickel ion, and in reaction system, cobalt ion and nickel ion are mainly with chelate
Form exists, and the sulfur remaining a small amount of cobalt ion and nickel ion and activation forms a small amount of nanocrystal, limits response speed,
Another part glucose molecule and derivant thereof can be adsorbed on the surface forming nanocrystal so that the growth of each crystal face is subject to
Arrived suppression, generating structure hydrogen storage more uniform, high activity unformed sulfide and be attached on the activation site of Graphene,
Along with the sulfide of the prolongation of hydro-thermal time, Graphene and attachment is collected as three-dimensional product and is attached to nickel foam by nickel sulfide
Surface, obtains nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material.Its specific surface area is relatively big, is 67～78m2/ g, system
Preparation Method is simple, and reaction time is short, it is not necessary to the later stage processes, and hydrogen storage property is high, can be directly used as hydrogen-storage electrode and be applied to electricity
Chemistry hydrogen storage field.
Accompanying drawing explanation
Fig. 1 is the nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material photo of test 1 preparation；
Fig. 2 is the nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material high power stereoscan photograph of test 1 preparation
Fig. 3 is the XRD spectra of the nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material of test 1 preparation；
Fig. 4 is the nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material charging and discharging curve of test 1 preparation；
Fig. 5 is the nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material photo of test 2 preparation；
Fig. 6 is the nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material high power stereoscan photograph of test 2 preparation
Fig. 7 is the XRD spectra of the nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material of test 2 preparation；
Fig. 8 is the nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material charging and discharging curve of test 2 preparation.
Detailed description of the invention
Detailed description of the invention one: the preparation side of a kind of nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material of present embodiment
Method sequentially includes the following steps:
One, preparing graphene oxide dispersion soln by Hummers method, regulation concentration is 1.8～2.2mg/ml；
Two, by cobalt acetate and sulfur with mol ratio as 1:(3～4) join in graphene oxide dispersion soln, continue stirring until all
Even, obtain mixed liquor；Wherein cobalt acetate is 1:(0.2～0.5 with the mass ratio of Graphene)；
Three, by ZrO2The mass ratio of abrading-ball and mixed liquor is 1:(15～20) ratio, by ZrO2Abrading-ball loads tool with mixed liquor
There is ZrO2In the ball grinder of liner, it is filled with high-purity argon gas, finally ball grinder is fixed in ball mill, at drum's speed of rotation be
Ball milling 4～8h under conditions of 500～700rpm, treat that ball milling terminates, and after ball grinder is cooled to room temperature, obtain mixed dispersion liquid；
Four, be 1:(2～4 by the ratio of width and water heating kettle diameter) nickel foam successively at deionization acetone, ethanol and deionization
Ultrasonic cleaning in water, after nickel foam being dried up with high-purity argon gas, then cleans 15～30 minutes with plasma washing machine；
Five, the mixed dispersion liquid that step 3 prepares is joined in water heating kettle, then press the mass ratio of glucose and mixed dispersion liquid
For 1:(100～120) add glucose, and the nickel foam after step 4 processes is immersed in mixed dispersion liquid,
180 DEG C～220 DEG C of Water Under thermal responses 18～24 hours；After reaction terminates, product is used deionized water drip washing, lyophilization
24～48 hours, obtain nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material.
Detailed description of the invention two: in present embodiment step one unlike detailed description of the invention one, graphene oxide dispersion is molten
In liquid, the concentration of graphene oxide is 2mg/ml；Other is identical with detailed description of the invention one.
Detailed description of the invention three: cobalt acetate and sulfur in present embodiment step 2 unlike detailed description of the invention one or two
Mol ratio is 1:3.5；Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: in present embodiment step 2 unlike one of detailed description of the invention one to three cobalt acetate with
The mass ratio of Graphene is 1:0.3；Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: ZrO in present embodiment step 3 unlike one of detailed description of the invention one to three2Abrading-ball
It is 1:18 with the mass ratio of mixed liquor；Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention six: nickel foam width in present embodiment step 4 unlike one of detailed description of the invention one to four
Spending the ratio with water heating kettle diameter is 1:3；Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention seven: in present embodiment step 5 unlike one of detailed description of the invention one to six glucose with
The mass ratio of mixed dispersion liquid is 1:110；Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: hydrothermal temperature in present embodiment step 5 unlike one of detailed description of the invention one to seven
Being 200 DEG C, the hydro-thermal time is 20 hours；Other is identical with one of detailed description of the invention one to seven.
By following verification experimental verification beneficial effects of the present invention:
Test 1: the preparation method of a kind of nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material of this test is according to the following steps
Carry out:
One, preparing graphene oxide dispersion soln by Hummers method, regulation concentration is 2mg/ml；
Two, cobalt acetate and sulfur are joined in graphene oxide dispersion soln for 1:3 with mol ratio, continue stirring until uniformly,
To mixed liquor；
Three, by ZrO2Abrading-ball and the ratio that mass ratio is 1:18 of mixed liquor, by ZrO2Abrading-ball has ZrO with mixed liquor loading2
In the ball grinder of liner, it is filled with high-purity argon gas, finally ball grinder is fixed in ball mill, be 700rpm at drum's speed of rotation
Under conditions of ball milling 8h, treat that ball milling terminates, after ball grinder is cooled to room temperature, obtain mixed dispersion liquid；
Four, the nickel foam that ratio is 1:3 of width and water heating kettle diameter is super in deionization acetone, ethanol and deionized water successively
Sound cleans, and after nickel foam being dried up with high-purity argon gas, then cleans 30 minutes with plasma processing tools；
Five, the mixed dispersion liquid that step 3 prepares is joined in water heating kettle, then press the mass ratio of glucose and mixed dispersion liquid
Add glucose for 1:100, and the nickel foam after step 4 processes is immersed in mixed dispersion liquid, at 200 DEG C of Water Unders
Thermal response 24 hours；After reaction terminates, product is used deionized water drip washing, lyophilization 24 hours, obtains nickel sulfide/graphite
Alkene/cobalt sulfide three-dimensional composite hydrogen storage material.
Nickel sulfide/Graphene that this test obtains/cobalt sulfide three-dimensional composite hydrogen storage material as it is shown in figure 1, it will be seen from figure 1 that
The product obtained is 3-D solid structure.
High power stereoscan photograph such as Fig. 2 institute of nickel sulfide/Graphene that this test obtains/cobalt sulfide three-dimensional composite hydrogen storage material
Showing, in product, cobalt sulfide and nickel sulfide are Graphene distribution uniform in undefined structure, and product as can be seen from Figure 2.
The XRD spectra of nickel sulfide/Graphene that this test obtains/cobalt sulfide three-dimensional composite hydrogen storage material is as it is shown on figure 3, from figure
3, it can be seen that the diffraction peaks broadening of product is serious, illustrate that product is unformed shape.
The charging and discharging curve of nickel sulfide/Graphene that this test obtains/cobalt sulfide three-dimensional composite hydrogen storage material as shown in Figure 4, from figure
4 can be seen that the hydrogen storage content of this three-dimensional composite hydrogen storage material is 2.3wt%.
Test 2: the preparation method of a kind of nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material of this test is according to the following steps
Carry out:
One, preparing graphene oxide dispersion soln by Hummers method, regulation concentration is 2.2mg/ml；
Three, cobalt acetate and sulfur are joined in graphene oxide dispersion soln for 1:4 with mol ratio, continue stirring until uniformly,
To mixed liquor；
Three, by ZrO2Abrading-ball and the ratio that mass ratio is 1:20 of mixed liquor, by ZrO2Abrading-ball has ZrO with mixed liquor loading2
In the ball grinder of liner, it is filled with high-purity argon gas, finally ball grinder is fixed in ball mill, be 600rpm at drum's speed of rotation
Under conditions of ball milling 5h, treat that ball milling terminates, after ball grinder is cooled to room temperature, obtain mixed dispersion liquid；
Four, the nickel foam that ratio is 1:3 of width and water heating kettle diameter is super in deionization acetone, ethanol and deionized water successively
Sound cleans, and after nickel foam being dried up with high-purity argon gas, then cleans 30 minutes with plasma washing machine；
Five, the mixed dispersion liquid that step 3 prepares is joined in water heating kettle, then press the mass ratio of glucose and mixed dispersion liquid
Add glucose for 1:110, and the nickel foam after step 4 processes is immersed in mixed dispersion liquid, at 220 DEG C of Water Unders
Thermal response 24 hours；After reaction terminates, product is used deionized water drip washing, lyophilization 24 hours, obtains nickel sulfide/graphite
Alkene/cobalt sulfide three-dimensional composite hydrogen storage material.
Nickel sulfide/Graphene that this test obtains/cobalt sulfide three-dimensional composite hydrogen storage material as it is shown in figure 5, from fig. 5, it can be seen that
The product obtained is 3-D solid structure.
High power stereoscan photograph such as Fig. 6 institute of nickel sulfide/Graphene that this test obtains/cobalt sulfide three-dimensional composite hydrogen storage material
Showing, in product, cobalt sulfide and nickel sulfide are Graphene distribution uniform in undefined structure, and product as can be seen from Figure 6.
The XRD spectra of nickel sulfide/Graphene that this test obtains/cobalt sulfide three-dimensional composite hydrogen storage material is as it is shown in fig. 7, from figure
7, it can be seen that the diffraction peaks broadening of product is serious, illustrate that product is unformed shape.
The charging and discharging curve of nickel sulfide/Graphene that this test obtains/cobalt sulfide three-dimensional composite hydrogen storage material as shown in Figure 8, from figure
8 can be seen that the hydrogen storage content of this three-dimensional composite hydrogen storage material is 2.0wt%.
Claims (8)
1. the preparation method of nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material, it is characterised in that the method by with
Lower step is carried out:
One, preparing graphene oxide dispersion soln by Hummers method, regulation concentration is 1.8～2.2mg/ml；
Two, by cobalt acetate and sulfur with mol ratio as 1:(3～4) join in graphene oxide dispersion soln, continue stirring until all
Even, obtain mixed liquor；Wherein cobalt acetate is 1:(0.2～0.5 with the mass ratio of Graphene)；
Three, by ZrO2The mass ratio of abrading-ball and mixed liquor is 1:(15～20) ratio, by ZrO2Abrading-ball loads tool with mixed liquor
There is ZrO2In the ball grinder of liner, it is filled with high-purity argon gas, finally ball grinder is fixed in ball mill, at drum's speed of rotation be
Ball milling 4～8h under conditions of 500～700rpm, treat that ball milling terminates, and after ball grinder is cooled to room temperature, obtain mixed dispersion liquid；
Four, be 1:(2～4 by the ratio of width and water heating kettle diameter) nickel foam successively at deionization acetone, ethanol and deionization
Ultrasonic cleaning in water, after nickel foam being dried up with high-purity argon gas, then cleans 15～30 minutes with plasma washing machine；
Five, the mixed dispersion liquid that step 3 prepares is joined in water heating kettle, then press the mass ratio of glucose and mixed dispersion liquid
For 1:(100～120) add glucose, and the nickel foam after step 4 processes is immersed in mixed dispersion liquid,
180 DEG C～220 DEG C of Water Under thermal responses 18～24 hours；After reaction terminates, product is used deionized water drip washing, lyophilization
24～48 hours, obtain nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material.
The preparation method of a kind of nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material the most according to claim 1,
It is characterized in that in step one, in graphene oxide dispersion soln, the concentration of graphene oxide is 2.0mg/ml.
The preparation side of a kind of nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material the most according to claim 1 and 2
Method, it is characterised in that in step 2, cobalt acetate is 1:3.5 with the mol ratio of sulfur.
The preparation side of a kind of nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material the most according to claim 1 and 2
Method, it is characterised in that in step 2, cobalt acetate is 1:0.3 with the mass ratio of Graphene.
The preparation side of a kind of nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material the most according to claim 1 and 2
Method, it is characterised in that ZrO in step 32Abrading-ball is 1:18 with the mass ratio of mixed liquor.
The preparation side of a kind of nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material the most according to claim 1 and 2
Method, it is characterised in that in step 4, the ratio of nickel foam width and water heating kettle diameter is 1:3.
The preparation side of a kind of nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material the most according to claim 1 and 2
Method, it is characterised in that in step 5, glucose is 1:110 with the mass ratio of mixed dispersion liquid.
The preparation side of a kind of nickel sulfide/Graphene/cobalt sulfide three-dimensional composite hydrogen storage material the most according to claim 1 and 2
Method, it is characterised in that in step 5, hydrothermal temperature is 200 DEG C, the hydro-thermal time is 20 hours.
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| CN109411720A (en) * | 2018-09-30 | 2019-03-01 | 肇庆市华师大光电产业研究院 | A kind of lithium ion battery negative material and preparation method thereof |
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| CN109817917A (en) * | 2019-01-21 | 2019-05-28 | 河北科技师范学院 | A kind of three-dimensional globular conductive graphene/Co1-xThe preparation method of S composite material |
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| CN106841614A (en) * | 2017-01-19 | 2017-06-13 | 济南大学 | It is a kind of while with the preparation and application of two methods checking type immunosensor mutually |
| CN109411720A (en) * | 2018-09-30 | 2019-03-01 | 肇庆市华师大光电产业研究院 | A kind of lithium ion battery negative material and preparation method thereof |
| CN109817916A (en) * | 2019-01-21 | 2019-05-28 | 河北科技师范学院 | A kind of three-dimensional globular conductive graphene/Co9S8The preparation method of composite material |
| CN109817917A (en) * | 2019-01-21 | 2019-05-28 | 河北科技师范学院 | A kind of three-dimensional globular conductive graphene/Co1-xThe preparation method of S composite material |
| CN109817916B (en) * | 2019-01-21 | 2022-02-01 | 河北科技师范学院 | Three-dimensional spherical conductive graphene/Co9S8Method for preparing composite material |
| CN109967093A (en) * | 2019-04-17 | 2019-07-05 | 齐鲁工业大学 | The preparation method of catalyst is precipitated in a kind of spherical shape cobalt disulfide/carbon composite highly effective oxygen |
| CN110048106A (en) * | 2019-04-19 | 2019-07-23 | 陕西科技大学 | A kind of cobalt sulfide and multistage carbon nano-structured composite material and preparation method and application |
| CN113754311A (en) * | 2021-08-12 | 2021-12-07 | 河北科技师范学院 | Preparation method of antimony selenide sulfide thin film |
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