CN105895869B - A kind of nickel sulfide/Graphene/Co3S4The preparation method of three-dimensional composite hydrogen storage material - Google Patents
A kind of nickel sulfide/Graphene/Co3S4The preparation method of three-dimensional composite hydrogen storage material Download PDFInfo
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
A kind of nickel sulfide/Graphene/Co3S4The preparation method of three-dimensional composite hydrogen storage material, it is related to the method for preparing three-dimensional 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.This method：First, graphene oxide dispersion soln is prepared；2nd, cobalt acetate and sulphur are added to graphene oxide dispersion soln and prepare mixed liquor；3rd, ball milling prepares mixed dispersion liquid；4th, nickel foam cleaning；5th, mixed dispersion liquid is added in water heating kettle, adds glucose, and nickel foam is immersed in mixed dispersion liquid, after hydro-thermal reaction, by product cleaning, freeze-drying, obtains nickel sulfide/Graphene/Co3S4Three-dimensional composite hydrogen storage material.The composite hydrogen storage material specific surface area is 67~78m2/ 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 directly used as hydrogen-storage electrode and be applied to electrochemical hydrogen storage field.
Description
Technical field
The present invention relates to the method for three-dimensional composite hydrogen storage material, more particularly to a kind of preparation of electrochemical hydrogen storage electrode material
Method.
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/Co is provided3S4The preparation method of three-dimensional composite hydrogen storage material.
A kind of nickel sulfide/Graphene/Co of the invention3S4The preparation method of three-dimensional composite hydrogen storage material is entered according to the following steps
OK：
First, graphene oxide dispersion soln is prepared by Hummers methods, regulation concentration is 1.8-2.2mg/mL；
2nd, by cobalt acetate and sulphur with mol ratio be 1:(3~4) are added in graphene oxide dispersion soln, lasting stirring
To uniform, mixed liquor is obtained；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 (15~20), 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
4~8h 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 18~24 when；After reaction terminates, by product deionized water drip washing, freeze-drying 24~
48 hours, obtain nickel sulfide/Graphene/Co3S4Three-dimensional composite hydrogen storage material.
The present invention is with indissoluble thing --- and elemental sulfur prepares nickel sulfide/Graphene/Co as sulphur source using hydro-thermal method3S4It is three-dimensional
Composite hydrogen storage material, due to elemental sulfur, solubility is extremely low in aqueous, through mechanical milling process activate after, can in water-heat process with
Nickel source, cobalt source slowly react, and the unformed sulfide that generating structure is more uniform, hydrogen storage high is active is simultaneously attached to Graphene
On activation site, surfactant glucose is oxidized to pentose, glucuronic acid and glucoside etc. and spreads out in water-heat process
Biology, because glucose molecule and its derivative possess abundant hydroxyl and carboxyl, a part of glucose molecule and its derivative
Thing can form stable chelate with cobalt ions and nickel ion, and in reaction system, cobalt ions and nickel ion are main with chelate
Form is present, and remaining a small amount of cobalt ions and nickel ion form a small amount of nanocrystal with the sulphur of activation, limit reaction speed,
Another part glucose molecule and its derivative can be adsorbed on the surface for forming nanocrystal so that the growth of each crystal face is received
Suppression is arrived, the unformed sulfide that generating structure is more uniform, hydrogen storage high is active is simultaneously attached on the activation site of Graphene, with
The extension of hydro-thermal time, the sulfide of Graphene and attachment is collected as three-dimensional product and is attached to nickel foam table by nickel sulfide
Face, obtains nickel sulfide/Graphene/Co3S4Three-dimensional composite hydrogen storage material.Its specific surface area is larger, is 67~78m2/ g, preparation side
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 directly used as hydrogen-storage electrode and be applied to electrochemistry storage
Hydrogen field.
Brief description of the drawings
Fig. 1 is to test the 1 nickel sulfide/Graphene/Co for preparing3S4Three-dimensional composite hydrogen storage material photo；
Fig. 2 is to test the 1 nickel sulfide/Graphene/Co for preparing3S4Three-dimensional composite hydrogen storage material high power stereoscan photograph
Fig. 3 is to test the 1 nickel sulfide/Graphene/Co for preparing3S4The XRD spectra of three-dimensional composite hydrogen storage material；
Fig. 4 is to test the 1 nickel sulfide/Graphene/Co for preparing3S4Three-dimensional composite hydrogen storage material charging and discharging curve；
Fig. 5 is to test the 2 nickel sulfide/Graphene/Co for preparing3S4Three-dimensional composite hydrogen storage material photo；
Fig. 6 is to test the 2 nickel sulfide/Graphene/Co for preparing3S4Three-dimensional composite hydrogen storage material high power stereoscan photograph
Fig. 7 is to test the 2 nickel sulfide/Graphene/Co for preparing3S4The XRD spectra of three-dimensional composite hydrogen storage material；
Fig. 8 is to test the 2 nickel sulfide/Graphene/Co for preparing3S4Three-dimensional composite hydrogen storage material charging and discharging curve.
Specific embodiment
Specific embodiment one：A kind of nickel sulfide/Graphene/Co of present embodiment3S4The system of three-dimensional composite hydrogen storage material
Preparation Method is carried out according to the following steps：
First, graphene oxide dispersion soln is prepared by Hummers methods, regulation concentration is 1.8~2.2mg/mL；
2nd, by cobalt acetate and sulphur with mol ratio be 1:(3~4) are added in graphene oxide dispersion soln, lasting stirring
To uniform, mixed liquor is obtained；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 (15~20), 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
4~8h 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 18~24 hours；After reaction terminates, by product deionized water drip washing, freeze-drying 24
~48 hours, obtain nickel sulfide/Graphene/Co3S4Three-dimensional composite hydrogen storage material.
Specific embodiment two：Present embodiment and graphene oxide in step one unlike specific embodiment one point
The concentration for dissipating graphene oxide in solution is 2mg/mL；Other are identical with specific embodiment one.
Specific embodiment three：Present embodiment and cobalt acetate in step 2 unlike specific embodiment one or two with
The mol ratio of sulphur is 1:3.5；Other are identical with specific embodiment one or two.
Specific embodiment four：Acetic acid in step 2 unlike one of present embodiment and specific embodiment one to three
Cobalt is 1 with the mass ratio of Graphene:0.3；Other are identical with one of specific embodiment one to three.
Specific embodiment five：ZrO in step 3 unlike one of present embodiment and specific embodiment one to three2
Abrading-ball is 1 with the mass ratio of mixed liquor:18；Other are identical with one of specific embodiment one to three.
Specific embodiment six：Foam in step 4 unlike one of present embodiment and specific embodiment one to four
The ratio of nickel width and water heating kettle diameter is 1:3；Other are identical with one of specific embodiment one to four.
Specific embodiment seven：Grape in step 5 unlike one of present embodiment and specific embodiment one to six
Sugar is 1 with the mass ratio of mixed dispersion liquid:110；Other are identical with one of specific embodiment one to six.
Specific embodiment eight：Hydro-thermal in step 5 unlike one of present embodiment and specific embodiment one to seven
Temperature is 200 DEG C, and the hydro-thermal time is 20 hours；Other are identical with one of specific embodiment one to seven.
With following verification experimental verification beneficial effects of the present invention：
Experiment 1：A kind of nickel sulfide/Graphene/Co of this experiment3S4The preparation method of three-dimensional composite hydrogen storage material is by following
Step is carried out：
First, graphene oxide dispersion soln is prepared by Hummers methods, regulation concentration is 2mg/mL；
2nd, by cobalt acetate and sulphur with mol ratio be 1:3 are added in graphene oxide dispersion soln, continue stirring until
It is even, obtain mixed liquor；
3rd, by ZrO2Abrading-ball is 1 with the mass ratio of mixed liquor:18 ratio, 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 in drum's speed of rotation
Ball milling 8h 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:3 nickel foam is successively in deionization acetone, ethanol and deionized water
Middle ultrasonic cleaning, after with high-purity argon gas, nickel foam is dried up, then is cleaned 30 minutes with plasma processing tools；
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 add glucose, and in nickel foam immersion mixed dispersion liquid after being processed through step 4, in 200 DEG C of conditions
Lower hydro-thermal reaction 24 hours；After reaction terminates, by product deionized water drip washing, freeze-drying 24 hours obtains nickel sulfide/stone
Black alkene/Co3S4Three-dimensional composite hydrogen storage material.
Nickel sulfide/Graphene/Co that this experiment is obtained3S4Three-dimensional composite hydrogen storage material is as shown in figure 1, can from Fig. 1
Go out, the product for obtaining is 3-D solid structure.
Nickel sulfide/Graphene/Co that this experiment is obtained3S4High power stereoscan photograph such as Fig. 2 of three-dimensional composite hydrogen storage material
It is shown, Co in product as can be seen from Figure 23S4It is Graphene distribution uniform in undefined structure, and product with nickel sulfide.
Nickel sulfide/Graphene/Co that this experiment is obtained3S4The XRD spectra of three-dimensional composite hydrogen storage material is as shown in figure 3, from figure
3 as can be seen that the diffraction peaks broadening of product seriously, illustrates that product is unformed shape.
Nickel sulfide/Graphene/Co that this experiment is obtained3S4The charging and discharging curve of three-dimensional composite hydrogen storage material as shown in figure 4,
The hydrogen storage content of the three-dimensional composite hydrogen storage material is 2.3wt% as can be seen from Figure 4.
Experiment 2：A kind of nickel sulfide/Graphene/Co of this experiment3S4The preparation method of three-dimensional composite hydrogen storage material is by following
Step is carried out：
First, graphene oxide dispersion soln is prepared by Hummers methods, regulation concentration is 2.2mg/mL；
3rd, by cobalt acetate and sulphur with mol ratio be 1:4 are added in graphene oxide dispersion soln, continue stirring until
It is even, obtain mixed liquor；
3rd, by ZrO2Abrading-ball is 1 with the mass ratio of mixed liquor:20 ratio, 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 in drum's speed of rotation
Ball milling 5h under conditions of 600rpm, 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:3 nickel foam is successively in deionization acetone, ethanol and deionized water
Middle ultrasonic cleaning, after with high-purity argon gas, nickel foam is dried up, then is cleaned 30 minutes with plasma washing machine；
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 1:110 add glucose, and in nickel foam immersion mixed dispersion liquid after being processed through step 4, in 220 DEG C of conditions
Lower hydro-thermal reaction 24 hours；After reaction terminates, by product deionized water drip washing, freeze-drying 24 hours obtains nickel sulfide/stone
Black alkene/Co3S4Three-dimensional composite hydrogen storage material.
Nickel sulfide/Graphene/Co that this experiment is obtained3S4Three-dimensional composite hydrogen storage material is as shown in figure 5, can from Fig. 5
Go out, the product for obtaining is 3-D solid structure.
Nickel sulfide/Graphene/Co that this experiment is obtained3S4High power stereoscan photograph such as Fig. 6 of three-dimensional composite hydrogen storage material
It is shown, Co in product as can be seen from Figure 63S4It is Graphene distribution uniform in undefined structure, and product with nickel sulfide.
Nickel sulfide/Graphene/Co that this experiment is obtained3S4The XRD spectra of three-dimensional composite hydrogen storage material is as shown in fig. 7, from figure
7 as can be seen that the diffraction peaks broadening of product seriously, illustrates that product is unformed shape.
Nickel sulfide/Graphene/Co that this experiment is obtained3S4The charging and discharging curve of three-dimensional composite hydrogen storage material as shown in figure 8,
The hydrogen storage content of the three-dimensional composite hydrogen storage material is 2.0wt% as can be seen from Figure 8.
Claims (8)
1. a kind of nickel sulfide/Graphene/Co3S4The preparation method of three-dimensional composite hydrogen storage material, it is characterised in that the method is by following
Step is carried out：
First, graphene oxide dispersion soln is prepared by Hummers methods, regulation concentration is 1.8~2.2mg/mL；
2nd, by cobalt acetate and sulphur with mol ratio be 1:(3~4) are added in graphene oxide dispersion soln, are continued stirring until
It is even, 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 (15~20), 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
4~8h 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 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 18~24 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/Co3S4Three-dimensional composite hydrogen storage material.
2. a kind of nickel sulfide/Graphene/Co according to claim 13S4The preparation method of three-dimensional composite hydrogen storage material, its
The concentration for being characterised by graphene oxide in graphene oxide dispersion soln in step one is 2.0mg/mL.
3. a kind of nickel sulfide/Graphene/Co according to claim 1 and 23S4The preparation method of three-dimensional composite hydrogen storage material,
It is characterized in that cobalt acetate and the mol ratio of sulphur are 1 in step 2:3.5.
4. a kind of nickel sulfide/Graphene/Co according to claim 1 and 23S4The preparation method of three-dimensional composite hydrogen storage material,
It is characterized in that cobalt acetate and the mass ratio of Graphene are 1 in step 2:0.3.
5. a kind of nickel sulfide/Graphene/Co according to claim 1 and 23S4The preparation method of three-dimensional composite hydrogen storage material,
It is characterized in that ZrO in step 32Abrading-ball is 1 with the mass ratio of mixed liquor:18.
6. a kind of nickel sulfide/Graphene/Co according to claim 1 and 23S4The preparation method of three-dimensional composite hydrogen storage material,
It is characterized in that the ratio of nickel foam width and water heating kettle diameter is 1 in step 4:3.
7. a kind of nickel sulfide/Graphene/Co according to claim 1 and 23S4The preparation method of three-dimensional composite hydrogen storage material,
It is characterized in that glucose and the mass ratio of mixed dispersion liquid are 1 in step 5:110.
8. a kind of nickel sulfide/Graphene/Co according to claim 1 and 23S4The preparation method of three-dimensional composite hydrogen storage material,
It is characterized in that hydrothermal temperature is 200 DEG C in step 5, the hydro-thermal time is 20 hours.
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