CN105883939A - Preparation method for nickel sulfide/graphene/carbon nano tube/cobalt sulfide three-dimensional composite hydrogen storage material - Google Patents
Preparation method for nickel sulfide/graphene/carbon nano tube/cobalt sulfide three-dimensional composite hydrogen storage material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/11—Sulfides
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The invention provides a preparation method for a nickel sulfide/graphene/carbon nano tube/cobalt sulfide three-dimensional composite hydrogen storage material and relates to a method for preparing the composite hydrogen storage material. The method aims at solving the technical problem that an existing cobalt sulfide composite material cannot be used as an electrochemical hydrogen storage electrode. The preparation method includes the steps that 1, oxidized graphene/carbon nano tube dispersion liquid is prepared; 2, cobaltous acetate and sulfur are added into the oxidized graphene/carbon nano tube dispersion liquid, the mixture is stirred to be uniform, and mixed liquid is obtained; 3, the mixed liquid is ball-milled; 4, foamed nickel is washed; 5, the mixed dispersion liquid is added into a hydrothermal kettle, glucose is added, foamed nickel is soaked in the mixed dispersion liquid, and a hydrothermal reaction is conducted for 48-60 h at the temperature of 180-220 DEG C; after the reaction is over, leaching and freeze drying are conducted, and the nickel sulfide/graphene/carbon nano tube/cobalt sulfide three-dimensional composite hydrogen storage material is obtained. The specific area of the composite hydrogen storage material ranges from 70 m<2>/g to 81 m<2>/g, and the composite hydrogen storage material can be used as the hydrogen storage electrode.
Description
Technical field
The present invention relates to a kind of method preparing cobalt sulfide/graphene/carbon nano-tube/nickel sulfide three-dimensional composite hydrogen storage material, especially
Relate to the preparation method of a kind of electrochemical hydrogen storage electrode material.
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/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material.
The preparation method of a kind of nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material of the present invention presses following step
Suddenly carry out:
One, preparing graphene oxide dispersion soln by Hummers method, regulation concentration is 2.2～2.5mg/ml, adds carbon and receives
Mitron mix homogeneously, obtains graphene oxide/carbon nano tube dispersion liquid；Wherein CNT with the mass ratio of graphene oxide is
1:(1～1.5)；
Two, by cobalt acetate and sulfur with mol ratio as 1:(3～4) join in graphene oxide/carbon nano tube dispersion liquid, persistently stir
Mix to uniformly, 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:(10～15) 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 24～36h 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 48～60 hours；After reaction terminates, product is used deionized water drip washing, lyophilization
24～48 hours, obtain nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material.
In the nickel sulfide/graphene/carbon nano-tube of the present invention/cobalt sulfide three-dimensional composite hydrogen storage material, nickel foam is both as hydrogen-storage electrode
The collector of material also serves as nickel source, and cobalt acetate, as cobalt source, uses the sulfur source elemental sulfur of indissoluble, only pass through simply,
It is easy to the ball milling of manipulation, by raw material fast activatings such as elemental sulfur and cobalt source, Graphene and CNTs, then nickel foam is soaked
Bubble carries out water-heat process after adding a certain amount of glucose in actived slurry, activated after elemental sulfur slowly and nickel source and sulfur
Source reaction grows the unformed sulfur product with more avtive spot, and then obtains the nickel sulfide/Graphene of high-specific surface area
/ CNT/cobalt sulfide three-dimensional composite hydrogen storage material.The present invention is by setting the material choice of hydrogen storage material and compound reaction
Meter, it is possible to give full play to the respective feature of these materials, improves the hydrogen storage property of composite hydrogen storage material further.
The present invention as sulfur source, utilizes hydro-thermal method to prepare nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three with the elemental sulfur of indissoluble
Dimension composite hydrogen storage material, owing to elemental sulfur dissolubility in aqueous is extremely low, after mechanical milling process activates, can be at water-heat process
In slowly react with nickel source, cobalt source, in water-heat process, surfactant glucose is oxidized to pentose, glucal
The derivants such as acid and glucoside, because glucose molecule and derivant thereof have abundant hydroxyl and carboxyl, so a part of Portugal
Grape glycan molecule and derivant thereof can form stable chelate, in reaction system, cobalt ion and nickel with cobalt ion and nickel ion
Ion mainly exists with chelate, and the sulfur remaining a small amount of cobalt ion and nickel ion and activation forms a small amount of nanocrystal,
Limit response speed, another part glucose molecule and derivant thereof and can adsorb on the surface forming nanocrystal so that
The growth of each crystal face is inhibited, generating structure hydrogen storage more uniform, high activity unformed sulfide and be attached to graphite
On the activation site of alkene, along with the sulfide of the prolongation of hydro-thermal time, Graphene and CNT and attachment is collected as three-dimensional product
Thing is also attached to nickel foam surface, the specific surface area of this nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material
Relatively big, it is 70～81m2/ g, 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 direct
It is applied to electrochemical hydrogen storage field as hydrogen-storage electrode.
Accompanying drawing explanation
Fig. 1 is the nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material photo of test 1 preparation；
Fig. 2 is the nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material high power scanning electron microscope of test 1 preparation
Photo
Fig. 3 is the XRD spectra of the nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material of test 1 preparation；
Fig. 4 is the nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material charging and discharging curve of test 1 preparation；
Fig. 5 is the nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material photo of test 2 preparation；
Fig. 6 is the nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material high power scanning electron microscope of test 2 preparation
Photo
Fig. 7 is the XRD spectra of the nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material of test 2 preparation；
Fig. 8 is the nickel sulfide/graphene/carbon nano-tube/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: a kind of nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material of present embodiment
Preparation method sequentially include the following steps:
One, preparing graphene oxide dispersion soln by Hummers method, regulation concentration is 2.2～2.5mg/ml, adds carbon and receives
Mitron mix homogeneously, obtains graphene oxide/carbon nano tube dispersion liquid；Wherein CNT with the mass ratio of graphene oxide is
1:(1～1.5)；
Two, by cobalt acetate and sulfur with mol ratio as 1:(3～4) join in graphene oxide/carbon nano tube dispersion liquid, persistently stir
Mix to uniformly, 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:(10～15) 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 24～36h 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 48～60 hours；After reaction terminates, product is used deionized water drip washing, lyophilization
24～48 hours, obtain nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material.
Detailed description of the invention two: the graphene oxide dispersion in present embodiment step one unlike detailed description of the invention one
The concentration of solution is 2.4mg/ml.Other is identical with detailed description of the invention one.
Detailed description of the invention three: the CNT in present embodiment step one unlike detailed description of the invention one or two with
The mass ratio of graphene oxide is 1:1.2.Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: the carbon nanometer in present embodiment step one unlike one of detailed description of the invention one to three
Pipe is 1:1.4 with the mass ratio of graphene oxide.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: in present embodiment step 2 unlike one of detailed description of the invention one to four cobalt acetate and
Sulfur is with mol ratio as 1:3.5.Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: in present embodiment step 2 unlike one of detailed description of the invention one to five 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 five.
Detailed description of the invention seven: present embodiment is the height described in step 3 unlike one of detailed description of the invention one to six
The percent mass purity of pure argon is more than 99.999%.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: nickel foam in present embodiment step 4 unlike one of detailed description of the invention one to seven
The ratio of width and water heating kettle diameter is 1:3.Other is identical with one of detailed description of the invention one to seven.
Detailed description of the invention nine: in present embodiment step 5 unlike one of detailed description of the invention one to eight glucose sugar with
The mass ratio of mixed dispersion liquid is 1:110.Other is identical with one of detailed description of the invention one to eight.
Detailed description of the invention ten: hydrothermal temperature in present embodiment step 5 unlike one of detailed description of the invention one to nine
Being 200 DEG C, the hydro-thermal time is 55 hours.Other is identical with one of detailed description of the invention one to nine.
By following verification experimental verification beneficial effects of the present invention:
Test 1: the preparation method of a kind of nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material of this test is pressed
Following steps are carried out:
One, preparing graphene oxide dispersion soln by Hummers method, regulation concentration is 2.3mg/ml, adds carbon nanometer
Pipe mix homogeneously, obtains graphene oxide/carbon nano tube dispersion liquid；Wherein CNT with the mol ratio of graphene oxide is
1:1.2；
Two, the cobalt acetate of 0.001mol and the sulfur of 0.0035mol are joined in 20ml graphene oxide/carbon nano tube dispersion liquid,
Continuously stirred 30min, obtains mixed liquor；
Three, by the ZrO of 2g2Mixed liquor loading prepared by abrading-ball and step 2 has ZrO2In the ball grinder of liner, it is filled with high-purity
Argon, is finally fixed on ball grinder in ball mill, ball milling 30h under conditions of drum's speed of rotation is 600rpm, treats that ball milling is tied
Bundle, after ball grinder is cooled to room temperature, obtains mixed dispersion liquid；
Four, by nickel foam ultrasonic cleaning 60 minutes in deionization acetone, ethanol and deionized water successively that width is 12mm；
After nickel foam being dried up with high-purity argon gas, then clean 30 minutes with plasma washing machine；
Five, the mixed dispersion liquid that step 3 prepares is joined in the water heating kettle that internal diameter is 25mm, adds 0.2g glucose,
And the nickel foam after step 4 processes is immersed in mixed dispersion liquid, 200 DEG C of Water Under thermal responses 50 hours；Reaction knot
Shu Hou, naturally cools to room temperature, and product is used deionized water drip washing, lyophilization 30 hours, obtain nickel sulfide/Graphene/
CNT/cobalt sulfide three-dimensional composite hydrogen storage material.
Nickel sulfide/graphene/carbon nano-tube that this test obtains/cobalt sulfide three-dimensional composite hydrogen storage material is as it is shown in figure 1, from Fig. 1
It can be seen that the product obtained is 3-D solid structure.
The high power stereoscan photograph of nickel sulfide/graphene/carbon nano-tube that this test obtains/cobalt sulfide three-dimensional composite hydrogen storage material
As in figure 2 it is shown, cobalt sulfide and nickel sulfide are Graphene and carbon in undefined structure, and product in product as can be seen from Figure 2
Nanotube distribution uniform.
XRD spectra such as Fig. 3 institute of nickel sulfide/graphene/carbon nano-tube that this test obtains/cobalt sulfide three-dimensional composite hydrogen storage material
Show, from figure 3, it can be seen that the diffraction peaks broadening of product is serious, illustrate that product is unformed shape.
Charging and discharging curve such as Fig. 4 of nickel sulfide/graphene/carbon nano-tube that this test obtains/cobalt sulfide three-dimensional composite hydrogen storage material
Shown in, the hydrogen storage content of this three-dimensional composite hydrogen storage material is 2.7wt% as can be seen from Figure 4.
Test 2: the preparation method of a kind of nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material of this test is pressed
Following steps are carried out:
One, preparing graphene oxide dispersion soln by Hummers method, regulation concentration is 2.5mg/ml, adds carbon nanometer
Pipe mix homogeneously, obtains graphene oxide/carbon nano tube dispersion liquid；Wherein CNT is 1:1 with the mass ratio of graphene oxide；
Two, the cobalt acetate of 0.001mol and the sulfur of 0.004mol are joined in the graphene oxide/carbon nano tube dispersion liquid of 20ml,
Continuously stirred 30min, obtains mixed liquor；Wherein cobalt acetate is 1:(0.2～0.5 with the mass ratio of Graphene)；
Three, by the ZrO of 1.8g2Abrading-ball has ZrO with mixed liquor loading2In the ball grinder of liner, being filled with percent mass purity is
The high-purity argon gas of 99.999%, is finally fixed on ball grinder in ball mill, ball milling under conditions of drum's speed of rotation is 700rpm
30h, treats that ball milling terminates, and after ball grinder is cooled to room temperature, obtains mixed dispersion liquid；
Four, by nickel foam ultrasonic cleaning 60 minutes in deionization acetone, ethanol and deionized water successively that width is 10mm；
After nickel foam being dried up with high-purity argon gas, then clean 30 minutes with plasma washing machine；
Five, the mixed dispersion liquid that step 3 prepares is joined in the water heating kettle that internal diameter is 25mm, adds 0.18g glucose,
And the nickel foam after step 4 processes is immersed in mixed dispersion liquid, 200 DEG C of Water Under thermal responses 55 hours；Reaction knot
Shu Hou, naturally cools to room temperature, and product is used deionized water drip washing, lyophilization 40 hours, obtain nickel sulfide/Graphene/
CNT/cobalt sulfide three-dimensional composite hydrogen storage material.
Nickel sulfide/graphene/carbon nano-tube that this test obtains/cobalt sulfide three-dimensional composite hydrogen storage material is as it is shown in figure 5, from Fig. 5
It can be seen that the product obtained is 3-D solid structure.
The high power stereoscan photograph of nickel sulfide/graphene/carbon nano-tube that this test obtains/cobalt sulfide three-dimensional composite hydrogen storage material
As shown in Figure 6, cobalt sulfide and nickel sulfide are Graphene and carbon in undefined structure, and product in product as can be seen from Figure 6
Nanotube distribution uniform.
XRD spectra such as Fig. 7 institute of nickel sulfide/graphene/carbon nano-tube that this test obtains/cobalt sulfide three-dimensional composite hydrogen storage material
Show, from figure 7 it can be seen that the diffraction peaks broadening of product is serious, illustrate that product is unformed shape.
Charging and discharging curve such as Fig. 8 of nickel sulfide/graphene/carbon nano-tube that this test obtains/cobalt sulfide three-dimensional composite hydrogen storage material
Shown in, the hydrogen storage content of this three-dimensional composite hydrogen storage material is 3.1wt% as can be seen from Figure 8.
Claims (10)
1. the preparation method of nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material, it is characterised in that should
Method sequentially includes the following steps:
One, preparing graphene oxide dispersion soln by Hummers method, regulation concentration is 2.2～2.5mg/ml, adds carbon and receives
Mitron mix homogeneously, obtains graphene oxide/carbon nano tube dispersion liquid；Wherein CNT with the mass ratio of graphene oxide is
1:(1～1.5)；
Two, by cobalt acetate and sulfur with mol ratio as 1:(3～4) join in graphene oxide/carbon nano tube dispersion liquid, persistently stir
Mix to uniformly, 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:(10～15) 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 24～36h 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 sugar and mixed dispersion liquid
For 1:(100～120) add glucose, and the nickel foam after step process is immersed in mixed dispersion liquid, at 180 DEG C～220 DEG C
Water Under thermal response 48～60 hours；After reaction terminates, product is used deionized water drip washing, lyophilization 24～48 hours,
Obtain nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material.
The system of a kind of nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material the most according to claim 1
Preparation Method, it is characterised in that the concentration of the graphene oxide dispersion soln in step one is 2.4mg/ml.
A kind of nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material the most according to claim 1 and 2
Preparation method, it is characterised in that the mass ratio of the CNT in step one and graphene oxide is 1:1.2.
A kind of nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material the most according to claim 1 and 2
Preparation method, it is characterised in that the mass ratio of the CNT in step one and graphene oxide is 1:1.4.
A kind of nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material the most according to claim 1 and 2
Preparation method, it is characterised in that in step 2, cobalt acetate and sulfur are with mol ratio as 1:3.5.
A kind of nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material the most according to claim 1 and 2
Preparation method, it is characterised in that in step 2, the mass ratio of cobalt acetate and Graphene is 1:0.3.
A kind of nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material the most according to claim 1 and 2
Preparation method, it is characterised in that the percent mass purity of the high-purity argon gas described in step 3 be more than 99.999%.
A kind of nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material the most according to claim 1 and 2
Preparation method, it is characterised in that in step 4, the width of nickel foam and the ratio of water heating kettle diameter are 1:3.
A kind of nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen storage material the most according to claim 1 and 2
Preparation method, it is characterised in that in step 5, the mass ratio of glucose and mixed dispersion liquid is 1:110.
A kind of nickel sulfide/graphene/carbon nano-tube/cobalt sulfide three-dimensional composite hydrogen-storage material the most according to claim 1 and 2
The preparation method of material, it is characterised in that in step 5, hydrothermal temperature is 200 DEG C, and the hydro-thermal time is 55 hours.
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| 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 |
| CN111744502A (en) * | 2020-07-07 | 2020-10-09 | 东华大学 | Magnesium-doped cobalt disulfide composite carbon nanotube material, preparation method and application |
| CN111864190A (en) * | 2019-04-26 | 2020-10-30 | 河南师范大学 | Preparation method of flexible sulfur positive electrode of lithium-sulfur battery |
| CN113130905A (en) * | 2021-04-16 | 2021-07-16 | 陕西科技大学 | Ultra-small cobalt sulfide nanosheet/carbon cloth composite material and preparation method thereof |
| CN113593923A (en) * | 2021-07-27 | 2021-11-02 | 新疆维吾尔自治区产品质量监督检验研究院 | Preparation method of cobalt sulfide/graphene-multiwalled carbon nanotube composite material, application of composite material in supercapacitor and testing method |
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| 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 |
| 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 |
| CN111864190A (en) * | 2019-04-26 | 2020-10-30 | 河南师范大学 | Preparation method of flexible sulfur positive electrode of lithium-sulfur battery |
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| CN111744502A (en) * | 2020-07-07 | 2020-10-09 | 东华大学 | Magnesium-doped cobalt disulfide composite carbon nanotube material, preparation method and application |
| CN113130905A (en) * | 2021-04-16 | 2021-07-16 | 陕西科技大学 | Ultra-small cobalt sulfide nanosheet/carbon cloth composite material and preparation method thereof |
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