CN105883939B - A kind of nickel sulfide/graphene/carbon nano-tube/Co3S4The preparation method of three-dimensional composite hydrogen storage material - Google Patents

A kind of nickel sulfide/graphene/carbon nano-tube/Co3S4The preparation method of three-dimensional composite hydrogen storage material Download PDF

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CN105883939B
CN105883939B CN201610216355.3A CN201610216355A CN105883939B CN 105883939 B CN105883939 B CN 105883939B CN 201610216355 A CN201610216355 A CN 201610216355A CN 105883939 B CN105883939 B CN 105883939B
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storage material
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韩璐
曹栋
张志伟
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Hebei Normal University of Science and Technology
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    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/11Sulfides
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/80Particles consisting of a mixture of two or more inorganic phases

Abstract

A kind of nickel sulfide/graphene/carbon nano-tube/Co3S4The preparation method of three-dimensional composite hydrogen storage material, the method the present invention relates to prepare composite hydrogen storage material, the present invention is to solve the technical problem that existing vulcanization cobalt composite material cannot act as electrochemical hydrogen storage electrode.Preparation method:First, graphene oxide/carbon nano tube dispersion liquid is prepared;2nd, cobalt acetate and sulphur are added in graphene oxide/carbon nano tube dispersion liquid and are stirred, obtain mixed liquor;3rd, by mixed liquor ball milling;4th, nickel foam is cleaned;5th, mixed dispersion liquid is added in water heating kettle, adds glucose, and nickel foam is immersed in mixed dispersion liquid, the hydro-thermal reaction 48~60 hours under the conditions of 180 DEG C~220 DEG C;After reaction terminates, drip washing, freeze-drying obtains nickel sulfide/graphene/carbon nano-tube/Co3S4Three-dimensional composite hydrogen storage material.The specific surface area of the composite hydrogen storage material is 70~81m2/ g, can be used as hydrogen-storage electrode.

Description

A kind of nickel sulfide/graphene/carbon nano-tube/Co3S4The system of three-dimensional composite hydrogen storage material Preparation Method
Technical field
Co is prepared the present invention relates to one kind3S4The method of/graphene/carbon nano-tube/nickel sulfide three-dimensional composite hydrogen storage material, More particularly to a kind of preparation method of electrochemical hydrogen storage electrode material.
Background technology
Energy crisis and environmental pollution have become global problem, in order to realize the sustainable development of society, the world Various countries continue to increase the exploitation of new energy, to obtain the free of contamination energy of high-efficiency cleaning.Hydrogen Energy is because with highest in new energy Energy matter ratio, the advantage such as cleanliness without any pollution during use, its development and utilization obtained extensive concern.But Hydrogen Energy is difficult to deposit Storage, scientific research personnel has found that solid hydrides can realize the reversible utilization of Hydrogen Energy by electrochemical means by long-term research, in It is that the research emphasis of hydrogen storage technology have turned to the exploitation of solid hydrogen storage material.
In recent years, before the metal nickel sulfide and cobalt sulfide of various nanostructureds are found to have good electrochemical hydrogen storage Scape, but the powder hydrogen storage material for obtaining needs the auxiliary materials such as addition conductive agent, binding agent to be coated with electrode process is prepared On collector, take time and effort electrode production process and increased the contact resistance of electrode, cause high magnification hydrogen storage property It is deteriorated, additionally, conductive agent, binding agent and current collector can increase the gross mass of electrode in itself so that electrode entirety specific capacity reduction It is many.Therefore, finding a kind of high power capacity and the composite hydrogen-storing electrode material of good stability of having concurrently turns into the key for developing.
In the prior art, the Chinese patent of Application No. 201310438808 discloses a kind of nickel foam --- the sulphur of nanometer eight Change nine cobalt composite materials and preparation method thereof, a kind of Ni-based eight vulcanization nine is directly obtained by ionic reaction using cobalt salt and urea Cobalt nano-tube array electrode material for super capacitor, but eight nine cobalts of vulcanization are two kinds of solvable predecessors by abundant in this kind of material The nano-tube array that ionic reaction is obtained, if directly using it as electrochemical hydrogen bearing material, its hydrogen storage property is relatively low.Application number Chinese patent for 201510307149.9 discloses one kind and prepares metal sulfide/Graphene/vulcanization nickel composite film Method, sulphur source is still solvable thiocarbamide or vulcanized sodium, and the product for finally giving is film, and specific surface area is smaller, therefore uncomfortable Conjunction is directly applied to electrochemical hydrogen storage field.
In order to obtain the 3-D solid structure of the more excellent stabilization of combination property and with the electrochemistry in high activity site Hydrogen storage material, to meet the application requirement that new technology and frontier are increasingly improved to it, just as association area urgent need to resolve Technical problem.
The content of the invention
The present invention is to solve the technical problem that existing vulcanization cobalt composite material cannot act as electrochemical hydrogen storage electrode, and A kind of nickel sulfide/graphene/carbon nano-tube/Co is provided3S4The preparation method of three-dimensional composite hydrogen storage material.
A kind of nickel sulfide/graphene/carbon nano-tube/Co of the invention3S4The preparation method of three-dimensional composite hydrogen storage material press with Lower step is carried out:
First, graphene oxide dispersion soln is prepared by Hummers methods, regulation concentration is 2.2~2.5mg/mL, is added CNT is well mixed, and obtains graphene oxide/carbon nano tube dispersion liquid;The wherein quality of CNT and graphene oxide Than being 1:(1~1.5);
2nd, by cobalt acetate and sulphur with mol ratio be 1:(3~4) are added in graphene oxide/carbon nano tube dispersion liquid, are held It is continuous to be stirred until homogeneous, obtain mixed liquor;Wherein cobalt acetate and the mass ratio of Graphene is 1:(0.2~0.5);
3rd, by ZrO2Abrading-ball is 1 with the mass ratio of mixed liquor:The ratio of (10~15), by ZrO2Abrading-ball loads with mixed liquor With ZrO2In the ball grinder of liner, high-purity argon gas are filled with, finally ball grinder is fixed in ball mill, be in drum's speed of rotation 24~36h of ball milling under conditions of 500~700rpm, treats that ball milling terminates, and after ball grinder is cooled to room temperature, obtains mixed dispersion liquid;
4th, it is 1 by the ratio of width and water heating kettle diameter:The nickel foam of (2~4) in deionization acetone, ethanol and is gone successively It is cleaned by ultrasonic in ionized water, after nickel foam is dried up with high-purity argon gas, then is cleaned with plasma washing machine 15~30 minutes;
5th, mixed dispersion liquid obtained in step 3 is added in water heating kettle, then by glucose and the matter of mixed dispersion liquid Amount is than being 1:(100~120) glucose is added, and in nickel foam immersion mixed dispersion liquid after being processed through step 4,180 DEG C~220 DEG C under the conditions of hydro-thermal reaction 48~60 hours;After reaction terminates, by product deionized water drip washing, freeze-drying 24 ~48 hours, obtain nickel sulfide/graphene/carbon nano-tube/Co3S4Three-dimensional composite hydrogen storage material.
Nickel sulfide/graphene/carbon nano-tube/Co of the invention3S4Nickel foam is both as hydrogen storage in three-dimensional composite hydrogen storage material The collector of electrode material also serves as nickel source, cobalt acetate as cobalt source, using the sulphur source of indissoluble --- elemental sulfur, only by letter Ball milling that is single, being easy to manipulation, by raw material fast activatings such as elemental sulfur and cobalt source, Graphene and CNTs, then by nickel foam Be immersed in actived slurry and add the laggard water-filling thermal process of a certain amount of glucose, it is activated after elemental sulfur slowly with nickel source and Sulphur source reaction grows the unformed sulfur product with more avtive spot, and then obtains the nickel sulfide/stone of high-specific surface area Black alkene/CNT/Co3S4Three-dimensional composite hydrogen storage material.The present invention is selected by the raw material to hydrogen storage material and recombination reaction is entered Row design, can give full play to the respective feature of these materials, further improve the hydrogen storage property of composite hydrogen storage material.
The present invention with the elemental sulfur of indissoluble as sulphur source, using hydro-thermal method prepare nickel sulfide/graphene/carbon nano-tube/ Co3S4Three-dimensional composite hydrogen storage material, due to elemental sulfur, solubility is extremely low in aqueous, after being activated through mechanical milling process, can be in hydro-thermal During slowly reacted with nickel source, cobalt source, surfactant glucose is oxidized to pentose, glucose in water-heat process The derivative such as aldehydic acid and glucoside, it is a part of because glucose molecule and its derivative possess abundant hydroxyl and carboxyl Glucose molecule and its derivative can form stable chelate with cobalt ions and nickel ion, in reaction system, cobalt ions and Nickel ion is main to be existed with chelate, and remaining a small amount of cobalt ions and nickel ion and the sulphur for activating form a small amount of nanocrystalline Core, limits reaction speed, and another part glucose molecule and its derivative can be adsorbed on the surface for forming nanocrystal, made The growth for obtaining each crystal face is inhibited, and generating structure is more uniform, hydrogen storage activity high unformed sulfide is simultaneously attached to stone On the activation site of black alkene, with the extension of hydro-thermal time, Graphene and CNT and the sulfide of attachment are collected as three-dimensional Product is simultaneously attached to foam nickel surface, the nickel sulfide/graphene/carbon nano-tube/Co3S4The specific surface of three-dimensional composite hydrogen storage material Product is larger, is 70~81m2/ g, preparation method is simple, and reaction time is short, it is not necessary to which the later stage is processed, and hydrogen storage property is high, can be direct Electrochemical hydrogen storage field is applied to as hydrogen-storage electrode.
Brief description of the drawings
Fig. 1 is to test the 1 nickel sulfide/graphene/carbon nano-tube/Co for preparing3S4Three-dimensional composite hydrogen storage material photo;
Fig. 2 is to test the 1 nickel sulfide/graphene/carbon nano-tube/Co for preparing3S4Three-dimensional composite hydrogen storage material high power scanning electricity Mirror photo
Fig. 3 is to test the 1 nickel sulfide/graphene/carbon nano-tube/Co for preparing3S4The XRD spectra of three-dimensional composite hydrogen storage material;
Fig. 4 is to test the 1 nickel sulfide/graphene/carbon nano-tube/Co for preparing3S4Three-dimensional composite hydrogen storage material discharge and recharge is bent Line;
Fig. 5 is to test the 2 nickel sulfide/graphene/carbon nano-tube/Co for preparing3S4Three-dimensional composite hydrogen storage material photo;
Fig. 6 is to test the 2 nickel sulfide/graphene/carbon nano-tube/Co for preparing3S4Three-dimensional composite hydrogen storage material high power scanning electricity Mirror photo
Fig. 7 is to test the 2 nickel sulfide/graphene/carbon nano-tube/Co for preparing3S4The XRD spectra of three-dimensional composite hydrogen storage material;
Fig. 8 is to test the 2 nickel sulfide/graphene/carbon nano-tube/Co for preparing3S4Three-dimensional composite hydrogen storage material discharge and recharge is bent Line.
Specific embodiment
Specific embodiment one:A kind of nickel sulfide/graphene/carbon nano-tube/Co of present embodiment3S4The compound storage of three-dimensional The preparation method of hydrogen material is carried out according to the following steps:
First, graphene oxide dispersion soln is prepared by Hummers methods, regulation concentration is 2.2~2.5mg/mL, is added CNT is well mixed, and obtains graphene oxide/carbon nano tube dispersion liquid;The wherein quality of CNT and graphene oxide Than being 1:(1~1.5);
2nd, by cobalt acetate and sulphur with mol ratio be 1:(3~4) are added in graphene oxide/carbon nano tube dispersion liquid, are held It is continuous to be stirred until homogeneous, obtain mixed liquor;Wherein cobalt acetate and the mass ratio of Graphene is 1:(0.2~0.5);
3rd, by ZrO2Abrading-ball is 1 with the mass ratio of mixed liquor:The ratio of (10~15), by ZrO2Abrading-ball loads with mixed liquor With ZrO2In the ball grinder of liner, high-purity argon gas are filled with, finally ball grinder is fixed in ball mill, be in drum's speed of rotation 24~36h of ball milling under conditions of 500~700rpm, treats that ball milling terminates, and after ball grinder is cooled to room temperature, obtains mixed dispersion liquid;
4th, it is 1 by the ratio of width and water heating kettle diameter:The nickel foam of (2~4) in deionization acetone, ethanol and is gone successively It is cleaned by ultrasonic in ionized water, after nickel foam is dried up with high-purity argon gas, then is cleaned with plasma washing machine 15~30 minutes;
5th, mixed dispersion liquid obtained in step 3 is added in water heating kettle, then by glucose and the matter of mixed dispersion liquid Amount is than being 1:(100~120) glucose is added, and in nickel foam immersion mixed dispersion liquid after being processed through step 4,180 DEG C~220 DEG C under the conditions of hydro-thermal reaction 48~60 hours;After reaction terminates, by product deionized water drip washing, freeze-drying 24 ~48 hours, obtain nickel sulfide/graphene/carbon nano-tube/Co3S4Three-dimensional composite hydrogen storage material.
Specific embodiment two:Present embodiment and the graphene oxide in step one unlike specific embodiment one The concentration of dispersion soln is 2.4mg/mL.Other are identical with specific embodiment one.
Specific embodiment three:Present embodiment and the carbon nanometer in step one unlike specific embodiment one or two Pipe is 1 with the mass ratio of graphene oxide:1.2.Other are identical with specific embodiment one or two.
Specific embodiment four:Carbon in step one unlike one of present embodiment and specific embodiment one to three Nanotube is 1 with the mass ratio of graphene oxide:1.4.Other are identical with one of specific embodiment one to three.
Specific embodiment five:Acetic acid in step 2 unlike one of present embodiment and specific embodiment one to four Cobalt and sulphur with mol ratio be 1:3.5.Other are identical with one of specific embodiment one to four.
Specific embodiment six:Acetic acid in step 2 unlike one of present embodiment and specific embodiment one to five Cobalt is 1 with the mass ratio of Graphene:0.3.Other are identical with one of specific embodiment one to five.
Specific embodiment seven:Unlike one of present embodiment and specific embodiment one to six described in step 3 High-purity argon gas quality percent purity be more than 99.999%.Other are identical with one of specific embodiment one to six.
Specific embodiment eight:Foam in step 4 unlike one of present embodiment and specific embodiment one to seven The width of nickel and the ratio of water heating kettle diameter are 1:3.Other are identical with one of specific embodiment one to seven.
Specific embodiment nine:Glucose in step 5 unlike one of present embodiment and specific embodiment one to eight Sugar is 1 with the mass ratio of mixed dispersion liquid:110.Other are identical with one of specific embodiment one to eight.
Specific embodiment ten:Hydro-thermal in step 5 unlike one of present embodiment and specific embodiment one to nine Temperature is 200 DEG C, and the hydro-thermal time is 55 hours.Other are identical with one of specific embodiment one to nine.
With following verification experimental verification beneficial effects of the present invention:
Experiment 1:A kind of nickel sulfide/graphene/carbon nano-tube/Co of this experiment3S4The preparation side of three-dimensional composite hydrogen storage material Method is carried out according to the following steps:
First, graphene oxide dispersion soln is prepared by Hummers methods, regulation concentration is 2.3mg/mL, adds carbon and receives Mitron is well mixed, and obtains graphene oxide/carbon nano tube dispersion liquid;Wherein CNT is with the mol ratio of graphene oxide 1:1.2;
2nd, the sulphur of the cobalt acetate of 0.001mol and 0.0035mol is added to 20mL graphene oxides/CNT dispersion In liquid, 30min is persistently stirred, obtain mixed liquor;
3rd, by the ZrO of 2g2Abrading-ball loads with mixed liquor prepared by step 2 has ZrO2In the ball grinder of liner, height is filled with , finally be fixed on ball grinder in ball mill by pure argon, the ball milling 30h under conditions of drum's speed of rotation is 600rpm, treats ball milling Terminate, after ball grinder is cooled to room temperature, obtain mixed dispersion liquid;
4th, by width for the nickel foam of 12mm is cleaned by ultrasonic 60 points in deionization acetone, ethanol and deionized water successively Clock;After with high-purity argon gas, nickel foam is dried up, then cleaned with plasma washing machine 30 minutes;
5th, mixed dispersion liquid obtained in step 3 is added in the water heating kettle that internal diameter is 25mm, adds 0.2g grapes In sugar, and nickel foam immersion mixed dispersion liquid after being processed through step 4, hydro-thermal reaction 50 hours under the conditions of 200 DEG C;Instead After should terminating, room temperature is naturally cooled to, by product deionized water drip washing, freeze-drying 30 hours obtains nickel sulfide/graphite Alkene/CNT/Co3S4Three-dimensional composite hydrogen storage material.
Nickel sulfide/graphene/carbon nano-tube/Co that this experiment is obtained3S4Three-dimensional composite hydrogen storage material is as shown in figure 1, from figure 1 as can be seen that the product for obtaining is 3-D solid structure.
Nickel sulfide/graphene/carbon nano-tube/Co that this experiment is obtained3S4The high power ESEM of three-dimensional composite hydrogen storage material Photo is as shown in Fig. 2 Co in product as can be seen from Figure 23S4It is Graphene and carbon in undefined structure, and product with nickel sulfide Nanotube distribution uniform.
Nickel sulfide/graphene/carbon nano-tube/Co that this experiment is obtained3S4The XRD spectra of three-dimensional composite hydrogen storage material such as Fig. 3 It is shown, from figure 3, it can be seen that the diffraction peaks broadening of product is serious, illustrate that product is unformed shape.
Nickel sulfide/graphene/carbon nano-tube/Co that this experiment is obtained3S4The charging and discharging curve of three-dimensional composite hydrogen storage material is such as Shown in Fig. 4, the hydrogen storage content of the three-dimensional composite hydrogen storage material is 2.7wt% as can be seen from Figure 4.
Experiment 2:A kind of nickel sulfide/graphene/carbon nano-tube/Co of this experiment3S4The preparation side of three-dimensional composite hydrogen storage material Method is carried out according to the following steps:
First, graphene oxide dispersion soln is prepared by Hummers methods, regulation concentration is 2.5mg/mL, adds carbon and receives Mitron is well mixed, and obtains graphene oxide/carbon nano tube dispersion liquid;Wherein CNT is with the mass ratio of graphene oxide 1:1;
The 2nd, the sulphur of the cobalt acetate of 0.001mol and 0.004mol be added to the graphene oxide/CNT point of 20mL In dispersion liquid, 30min is persistently stirred, obtain mixed liquor;Wherein cobalt acetate and the mass ratio of Graphene is 1:(0.2~0.5);
3rd, by the ZrO of 1.8g2Abrading-ball loads with mixed liquor has ZrO2In the ball grinder of liner, quality percent purity is filled with It is 99.999% high-purity argon gas, finally ball grinder is fixed in ball mill, under conditions of drum's speed of rotation is 700rpm Ball milling 30h, treats that ball milling terminates, and after ball grinder is cooled to room temperature, obtains mixed dispersion liquid;
4th, by width for the nickel foam of 10mm is cleaned by ultrasonic 60 points in deionization acetone, ethanol and deionized water successively Clock;After with high-purity argon gas, nickel foam is dried up, then cleaned with plasma washing machine 30 minutes;
5th, mixed dispersion liquid obtained in step 3 is added in the water heating kettle that internal diameter is 25mm, adds 0.18g grapes In sugar, and nickel foam immersion mixed dispersion liquid after being processed through step 4, hydro-thermal reaction 55 hours under the conditions of 200 DEG C;Instead After should terminating, room temperature is naturally cooled to, by product deionized water drip washing, freeze-drying 40 hours obtains nickel sulfide/graphite Alkene/CNT/Co3S4Three-dimensional composite hydrogen storage material.
Nickel sulfide/graphene/carbon nano-tube/Co that this experiment is obtained3S4Three-dimensional composite hydrogen storage material is as shown in figure 5, from figure 5 as can be seen that the product for obtaining is 3-D solid structure.
Nickel sulfide/graphene/carbon nano-tube/Co that this experiment is obtained3S4The high power ESEM of three-dimensional composite hydrogen storage material Photo is as shown in fig. 6, Co in product as can be seen from Figure 63S4It is Graphene and carbon in undefined structure, and product with nickel sulfide Nanotube distribution uniform.
Nickel sulfide/graphene/carbon nano-tube/Co that this experiment is obtained3S4The XRD spectra of three-dimensional composite hydrogen storage material such as Fig. 7 It is shown, from figure 7 it can be seen that the diffraction peaks broadening of product is serious, illustrate that product is unformed shape.
Nickel sulfide/graphene/carbon nano-tube/Co that this experiment is obtained3S4The charging and discharging curve of three-dimensional composite hydrogen storage material is such as Shown in Fig. 8, the hydrogen storage content of the three-dimensional composite hydrogen storage material is 3.1wt% as can be seen from Figure 8.

Claims (10)

1. a kind of nickel sulfide/graphene/carbon nano-tube/Co3S4The preparation method of three-dimensional composite hydrogen storage material, it is characterised in that should Method is carried out according to the following steps:
First, graphene oxide dispersion soln is prepared by Hummers methods, regulation concentration is 2.2~2.5mg/mL, adds carbon and receives Mitron is well mixed, and obtains graphene oxide/carbon nano tube dispersion liquid;Wherein CNT is with the mass ratio of graphene oxide 1:(1~1.5);
2nd, by cobalt acetate and sulphur with mol ratio be 1:(3~4) are added in graphene oxide/carbon nano tube dispersion liquid, are persistently stirred Mix to uniform, obtain mixed liquor;Wherein cobalt acetate and the mass ratio of Graphene is 1:(0.2~0.5);
3rd, by ZrO2Abrading-ball is 1 with the mass ratio of mixed liquor:The ratio of (10~15), by ZrO2Abrading-ball loads with mixed liquor to be had ZrO2In the ball grinder of liner, high-purity argon gas are filled with, finally ball grinder is fixed in ball mill, be 500 in drum's speed of rotation 24~36h of ball milling under conditions of~700rpm, treats that ball milling terminates, and after ball grinder is cooled to room temperature, obtains mixed dispersion liquid;
4th, it is 1 by the ratio of width and water heating kettle diameter:The nickel foam of (2~4) is successively in deionization acetone, ethanol and deionization It is cleaned by ultrasonic in water, after nickel foam is dried up with high-purity argon gas, then is cleaned with plasma washing machine 15~30 minutes;
5th, mixed dispersion liquid obtained in step 3 is added in water heating kettle, then by glucose sugar and the mass ratio of mixed dispersion liquid It is 1:(100~120) add glucose, and in nickel foam immersion mixed dispersion liquid after being processed through step 4,180 DEG C~ Hydro-thermal reaction 48~60 hours under the conditions of 220 DEG C;After reaction terminates, by product deionized water drip washing, freeze-drying 24~48 Hour, obtain nickel sulfide/graphene/carbon nano-tube/Co3S4Three-dimensional composite hydrogen storage material.
2. a kind of nickel sulfide/graphene/carbon nano-tube/Co according to claim 13S4The system of three-dimensional composite hydrogen storage material Preparation Method, it is characterised in that the concentration of the graphene oxide dispersion soln in step one is 2.4mg/mL.
3. a kind of nickel sulfide/graphene/carbon nano-tube/Co according to claim 1 and 23S4Three-dimensional composite hydrogen storage material Preparation method, it is characterised in that CNT and the mass ratio of graphene oxide in step one are 1:1.2.
4. a kind of nickel sulfide/graphene/carbon nano-tube/Co according to claim 1 and 23S4Three-dimensional composite hydrogen storage material Preparation method, it is characterised in that CNT and the mass ratio of graphene oxide in step one are 1:1.4.
5. a kind of nickel sulfide/graphene/carbon nano-tube/Co according to claim 1 and 23S4Three-dimensional composite hydrogen storage material Preparation method, it is characterised in that the mol ratio of cobalt acetate and sulphur is 1 in step 2:3.5.
6. a kind of nickel sulfide/graphene/carbon nano-tube/Co according to claim 1 and 23S4Three-dimensional composite hydrogen storage material Preparation method, it is characterised in that cobalt acetate and the mass ratio of Graphene are 1 in step 2:0.3.
7. a kind of nickel sulfide/graphene/carbon nano-tube/Co according to claim 1 and 23S4Three-dimensional composite hydrogen storage material Preparation method, it is characterised in that the quality percent purity of the high-purity argon gas described in step 3 is more than 99.999%.
8. a kind of nickel sulfide/graphene/carbon nano-tube/Co according to claim 1 and 23S4Three-dimensional composite hydrogen storage material Preparation method, it is characterised in that the ratio of the width of nickel foam and water heating kettle diameter is 1 in step 4:3.
9. a kind of nickel sulfide/graphene/carbon nano-tube/Co according to claim 1 and 23S4Three-dimensional composite hydrogen storage material Preparation method, it is characterised in that glucose and the mass ratio of mixed dispersion liquid are 1 in step 5:110.
10. a kind of nickel sulfide/graphene/carbon nano-tube/Co according to claim 1 and 23S4Three-dimensional composite hydrogen storage material Preparation method, it is characterised in that in step 5 hydrothermal temperature be 200 DEG C, the hydro-thermal time be 55 hours.
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