CN106229493B - A kind of intercalation Co1-xThe preparation method of the graphene-based composite material of S - Google Patents
A kind of intercalation Co1-xThe preparation method of the graphene-based composite material of S Download PDFInfo
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
A kind of intercalation Co1‑xThe preparation method of the graphene-based composite material of S, it is related to the preparation method of graphene-based composite material.It is to solve existing Co1‑xThe technical problem that the hydrogen storage property of S and graphene composite material is poor, the performance under high intensity discharge electric current is low and cyclical stability is poor.The composite material of the present invention is by Co1‑xS and the compound sandwich layer structure of graphene, Co1‑xS is embedded among the lamella of graphene, wherein graphene and Co1‑XThe molar ratio of S is 1:(0.9~1.5).Preparation method：First graphene is mixed with sulphur powder, ball milling, then add cobalt powder mixed, ball milling, obtain intercalation Co1‑xThe graphene-based composite material of S.The material is made hydrogen-bearing alloy electrode its maximum hydrogen storage capability and reaches 3.73wt%, manufactured battery, and the hydrogen storage ability after cycle 50 times remains at 88% or more, can be used for hydrogen storage field.
Description
Technical field
The present invention relates to the preparation methods of graphene-based composite material.
Background technology
Reserves of the hydrogen in nature are extremely abundant, and there is highest energy matter ratio, cleanliness without any pollution to be expected to become the following energy
A kind of main clean energy resource in source, but Hydrogen Energy is not easy to store, it is difficult to it uses on a large scale, scientists pass through long-term research
It was found that some carbon materials, such as activated carbon, carbon nanotube and graphene can reversibly be stored hydrogen atom by electrochemical process
To wherein, people have carried out extensively the electrochemical hydrogen storage performance of a variety of different carbon materials of metal hydride surface modification at present
General research.Wherein, graphene is a kind of tightly packed carbonaceous new material at single layer bi-dimensional cellular shape lattice structure of carbon atom,
With high specific surface area, fabulous crystallinity and electric property are surface modified it and ideal answer can be obtained
Close hydrogen storage material.In numerous surface modification metal materials, Co base hydrogen storage systems have excellent electrochemical hydrogen storage performance and compared with
High hydrogen storage capability receives the extensive concern of numerous scientific research personnel, shows Co based hydrogen storage materials and non-gold by further investigation
Belong to element S and form compound, plays the role of raising for hydrogen storage property.Cobalt sulphur compound includes a series of atomic ratios
Compound, such as Co1-xS,CoS,CoS2,Co3S4,Co9S8Deng wherein Co1-xS has well because of its special deficient cobalt type structure
Hydrogen storage foreground.Therefore, Co is utilized1-xThe grapheme modified surfaces S, it will greatly improve hydrogen storage property.Obtain preferable surface modification
Effect, should be not only therebetween the mixing of physics, and should have chemistry key and, and Co1-xModification areas of the S to graphene
Bigger, effect is better, but current complex method is all by granular Co1-xThe graphene surface physics of S and multilayered structure is multiple
It closes, granular Co1-xS is equably scattered in multi-layer graphene surface, Co1-xS is not high to graphene surface degree of modification, can not
The chemical modification for accomplishing all to carry out each layer of graphene surface large area carries out hydrogen storage using the compound of this type and answers
With hydrogen storage property is undesirable, and the performance under high intensity discharge electric current is relatively low and cyclical stability is also poor.
Invention content
The present invention is to solve existing Co1-xThe hydrogen storage property of S and graphene composite material is poor, under high intensity discharge electric current
Performance is low and the technical problem of cyclical stability difference, and provide a kind of intercalation Co1-xThe graphene-based composite material of S
Preparation method.
The intercalation Co of the present invention1-xThe graphene-based composite material of S is by Co1-xS and the compound sandwich of graphene
Layer structure, Co1-xS is embedded among the lamella of graphene, wherein graphene and Co1-XThe molar ratio of S is 1:(0.9~
1.5)。
Above-mentioned intercalation Co1-xThe preparation method of the graphene-based composite material of S, carries out according to the following steps：
One, it is 1 according to molar ratio by graphene and sulphur powder:(1~1.5) is mixed, and mixed-powder I is obtained；
Two, ZrO is pressed2The mass ratio of abrading-ball and mixed-powder I is (18~20):1 ratio, by ZrO2Abrading-ball and mixed powder
End I, which is packed into, has ZrO2In the ball grinder of liner, it is filled with high-purity argon gas, finally ball grinder is fixed in ball mill, in ball milling
24~30h of ball milling after ball grinder is cooled to room temperature, obtains stone to the end of ball milling under conditions of machine rotating speed is 900~1000rpm
Black alkene/S/ graphene powders；
Three, the molar ratio for pressing S and Co in graphene/S/ graphene powders is 1:The graphite that (0.9~1) prepares step 2
Alkene/S/ graphene powders are mixed with cobalt powder, obtain mixed-powder II；
Four, ZrO is pressed2The mass ratio of abrading-ball and mixed-powder II is (10~15):1, by ZrO2Abrading-ball is put with mixed-powder II
Enter with ZrO2In the ball grinder of liner, it is filled with high-purity argon gas, finally ball grinder is fixed in ball mill, in drum's speed of rotation
For 24~30h of ball milling under conditions of 400~500rpm, to the end of ball milling, ball grinder is cooled to room temperature, and obtains intercalation
Co1-xThe graphene-based composite material of S.
The present invention uses high-energy ball milling method, higher rotating speed to allow the material to be come into full contact with, acted on and reacted,
Under high speed conditions, first using graphene and S as raw material, the abrading-ball of high speed makes internal energy drastically increase, first in mechanical milling process
First so that the fusing of powdered sulfur granules, liquid sulfur is attached to graphene film layer surface, and from the edge or fault location of graphene
Interlayer is penetrated into, graphene/S/ graphene sandwich structure composite materials are obtained, continues to carry out high-energy ball milling to the composite material,
So that the part sulphur of interlayer and the further chemical combination of active carbon atom in graphene, generate S-C keys, the generation of chemical bond is conducive to
The stabilization of structure and the transmission of electronics.It is further continued for mixing Co powder using high-energy ball milling, can be made by controlling ratio of grinding media to material and rotating speed
The S obtained between the graphene layer in graphene/S/ graphene composite materials generates Co with Co chemical combination1-xS obtains graphene/Co1-xS/
Graphene sandwich structure composite hydrogen storage material.This Co1-xS is embedded between graphene layer to the uniform big face in single-layer graphene surface
The material of product modification is by generating chemical bond and passing through the particle of the reversible transmission of chemical bond between interface so that the hydrogen storage property of material
It greatly improves.The composite hydrogen storage material can prepare hydrogen-bearing alloy electrode, be applied in the energy resource systems such as Ni-MH battery, maximum storage
Hydrogen capacity is had excellent performance up to 3.73wt%, electrochemical hydrogen storage.Intercalation Co1-xThe graphene-based composite material of S is prepared into electricity
Pond, after cycle 50 times, intercalation Co1-xThe hydrogen storage ability of the graphene-based composite material of S remains at 88% or more.Together
When under the conditions of the discharge current density of 1000mA/g, discharge capability remains at 80% or more.It can be used for hydrogen storage field.
The preparation process of the present invention is simple, safe.
Description of the drawings
Fig. 1 is to test the 1 intercalation Co prepared1-xThe transmission electron microscope photo of the graphene-based composite material of S；
Fig. 2 is to test the 1 intercalation Co prepared1-xThe XRD spectra of the graphene-based composite material of S；
Fig. 3 is to test the 1 intercalation Co prepared1-xThe XPS-C test results of the graphene-based composite material of S；
Fig. 4 is to test the 1 intercalation Co prepared1-xThe XPS-S test results of the graphene-based composite material of S；
Fig. 5 is to test the 1 intercalation Co prepared1-xThe stable circulation linearity curve of the graphene-based composite material of S；
Fig. 6 is to test the 1 intercalation Co prepared1-xThe high-rate discharge ability curve of the graphene-based composite material of S；
Fig. 7 is the stereoscan photograph of graphene composite hydrogen storage material prepared by contrast test 1；
Fig. 8 is the stereoscan photograph of graphene composite hydrogen storage material prepared by contrast test 2；
Fig. 9 is to test the 2 intercalation Co prepared1-xThe transmission electron microscope photo of the graphene-based composite material of S；
Figure 10 is to test the 2 intercalation Co prepared1-xThe stable circulation linearity curve of the graphene-based composite material of S；
Figure 11 is to test the 2 intercalation Co prepared1-xThe high-rate discharge ability curve of the graphene-based composite material of S；
Specific implementation mode
Specific implementation mode one：The intercalation Co of present embodiment1-xThe graphene-based composite material of S is by Co1-xS and
The compound sandwich layer structure of graphene, Co1-xS is embedded among the lamella of graphene, wherein graphene and Co1-XS's
Molar ratio is 1:(0.9~1.5).
Specific implementation mode two：Prepare the intercalation Co described in specific implementation mode one1-xThe graphene-based composite wood of S
The preparation method of material carries out according to the following steps：
One, it is 1 according to molar ratio by graphene and sulphur powder:(1~1.5) is mixed, and mixed-powder I is obtained；
Two, ZrO is pressed2The mass ratio of abrading-ball and mixed-powder I is (18~20):1 ratio, by ZrO2Abrading-ball and mixed powder
End I, which is packed into, has ZrO2In the ball grinder of liner, it is filled with high-purity argon gas, finally ball grinder is fixed in ball mill, in ball milling
24~30h of ball milling after ball grinder is cooled to room temperature, obtains stone to the end of ball milling under conditions of machine rotating speed is 900~1000rpm
Black alkene/S/ graphene powders；
Three, the molar ratio for pressing S and Co in graphene/S/ graphene powders is 1:The graphite that (0.9~1) prepares step 2
Alkene/S/ graphene powders are mixed with cobalt powder, obtain mixed-powder II；
Four, ZrO is pressed2The mass ratio of abrading-ball and mixed-powder II is (10~15):1, by ZrO2Abrading-ball is put with mixed-powder II
Enter with ZrO2In the ball grinder of liner, it is filled with high-purity argon gas, finally ball grinder is fixed in ball mill, in drum's speed of rotation
For 24~30h of ball milling under conditions of 400~500rpm, to the end of ball milling, ball grinder is cooled to room temperature, and obtains intercalation
Co1-xThe graphene-based composite material of S.
Specific implementation mode three：Present embodiment and the height unlike specific implementation mode two described in step 2 and four
Pure argon refers to the argon gas that mass percentage concentration is more than 99.999%.It is other to be identical with embodiment two.
Specific implementation mode four：In present embodiment step 1 unlike specific implementation mode two or three graphene with
Sulphur powder is 1 according to molar ratio:1.2 mixing.It is other identical as specific implementation mode two or three.
Specific implementation mode five：ZrO in step 2 unlike one of present embodiment and specific implementation mode two to four2
The mass ratio of abrading-ball and mixed-powder I is 19：1.It is other identical as one of specific implementation mode two to four.
Specific implementation mode six：Ball milling in step 2 unlike one of present embodiment and specific implementation mode two to five
Machine rotating speed is 950rpm, Ball-milling Time 28h.It is other identical as one of specific implementation mode two to five.
Specific implementation mode seven：S is pressed in step 3 unlike one of present embodiment and specific implementation mode two to six
Molar ratio with Co is 1:0.95 mixes sulphur powder with cobalt powder.It is other identical as one of specific implementation mode two to six.
Specific implementation mode eight：ZrO in step 4 unlike one of present embodiment and specific implementation mode two to seven2
The mass ratio of abrading-ball and mixed-powder II is 12：1.It is other identical as one of specific implementation mode two to seven.
Specific implementation mode nine：Ball milling in step 4 unlike one of present embodiment and specific implementation mode two to seven
Machine rotating speed is 450rpm, Ball-milling Time 28h.It is other identical as one of specific implementation mode two to seven.
With following verification experimental verification beneficial effects of the present invention：
Experiment 1：The intercalation Co of this experiment1-xThe preparation method of the graphene-based composite material of S, according to the following steps into
Row：
One, it is 1 according to molar ratio by graphene and sulphur powder:1 is mixed, and mixed-powder I is obtained；
Two, ZrO is pressed2The mass ratio of abrading-ball and mixed-powder I is 20:1 ratio, by ZrO2Abrading-ball is packed into mixed-powder I
With ZrO2In the ball grinder of liner, it is filled with the high-purity argon gas that mass percentage concentration is 99.999%, finally fixes ball grinder
In ball mill, drum's speed of rotation be 900rpm under conditions of ball milling for 24 hours, to the end of ball milling, after ball grinder is cooled to room temperature,
Obtain graphene/S/ graphene powders；
Three, the molar ratio for pressing S and Co in graphene/S/ graphene powders is 1:The graphite that (0.9~1) prepares step 2
Alkene/S/ graphene powders are mixed with cobalt powder, obtain mixed-powder II；
Four, ZrO is pressed2The mass ratio of abrading-ball and mixed-powder II is 15:1, by ZrO2Abrading-ball is put into mixed-powder II to be had
ZrO2In the ball grinder of liner, it is filled with the high-purity argon gas that mass percentage concentration is 99.999%, ball grinder is finally fixed on ball
In grinding machine, for 24 hours, to the end of ball milling, ball grinder is cooled to room temperature ball milling, obtains layer under conditions of drum's speed of rotation is 450rpm
Between embedded Co1-xThe graphene-based composite material of S.
The intercalation Co that this experiment obtains1-xThe transmission electron microscope photo of the graphene-based composite material of S as shown in Figure 1, from
It is sandwich layer structure, Co that Fig. 1, which can be seen that composite material,1-xS is embedded among graphene sheet layer, wherein graphene with
Co1-xThe molar ratio of S is 1：1.On the photo it can be seen that without individual Co1-xS particles and Sheet Graphite alkene exist, Co1-xS
With graphene under high-energy ball milling effect, it has been complex as a whole.
Fig. 2 is to test 1 obtained intercalation Co1-xThe XRD spectra of the graphene-based composite material of S, can from Fig. 2
Go out, composite material is by Co1-xS and graphene composition.
Fig. 3 is intercalation Co prepared by this experiment1-xThe XPS C elements analysis test of the graphene-based composite material of S
As a result, compared with original rGO, it is compound after material show typical C-S characteristic peaks (285.6eV), this illustrates Co1-xS
In S elements and rGO in C element chemical action has occurred, produce chemical bond.
Fig. 4 is intercalation Co prepared by this experiment1-xThe XPS S elemental analyses test knot of the graphene-based composite material of S
Fruit, with simple Co1-xS is compared, it is compound after material show that typical S-C characteristic peaks (163.6eV) also illustrate Co1-xS pairs
The success of rGO surface modifications.
The maximum hydrogen storage capability for the composite hydrogen storage material that this experiment obtains is 2.83wt%, and electrochemical hydrogen storage is had excellent performance.
Intercalation Co prepared by this experiment1-xThe method of the cyclical stability test of the graphene-based composite material of S is such as
Under：
(1) positive preparation：First by powdered Ni (OH)2With Co powder according to 8：It is equal that 1 mass ratio is ground mixing
It is even, the polytetrafluoroethylene (PTFE) (PTFE) of appropriate liquid state is then added.The nickel foam pressure of 50MPa wiped will be finally applied to suppress
At electrode, up to anode after drying at room temperature.
(2) preparation of cathode：By intercalation Co1-xThe graphene-based composite material and acetylene black of S is according to 7：2 quality
Than in mortar ground and mixed it is uniform after, the polytetrafluoroethylene (PTFE) that liquid state is added uniformly is coated onto in nickel foam, same 50 MPa
Pressure electrode pressing, after being dried at room temperature for battery cathode.
(3) electrolyte is the high concentration KOH solution of 6mol/L.
(4) battery test system step is set：Setting electrode, which immerses, first stands 3min in electrolyte.Then with 100
The density of charging current of mA/g carries out charging 10h to electrode material, stands 2min after charging complete before discharge to stablize electricity
Position, then 0V is discharged under the discharge current density of 30mA/g, the charge and discharge process so recycled.Finally use discharge current
The obtained numerical value of dosage of electric discharge total time active material again divided by electrode is multiplied by characterize total discharge capacity of electrode, it is single
Position is mAh/g.
The relation curve of cycle-index and hydrogen storage ability that cyclical stability test process obtains is as shown in figure 5, can from Fig. 5
To find out, after recycling 20 times, intercalation Co1-xThe hydrogen storage ability of the graphene-based composite material of S remains at 80% or more.
Test the intercalation Co of this experiment preparation1-xThe graphene-based composite material of S is in big discharge current density condition
Under, high-rate discharge capacity, obtained discharge current density and high-rate discharge capacity graph of relation as shown in fig. 6, from
Fig. 6 can be seen that under the conditions of discharge current density in 1000mA/g, and discharge capability remains at 80% or more.
Contrast test 1：This experiment is set as from the drum's speed of rotation in step 2 and step 4 unlike experiment 1
300rpm, other with 1 all same of experiment, obtained graphene composite hydrogen storage material.The scanning electron microscope of the composite hydrogen storage material is shone
Piece is as shown in fig. 7, from figure 7 it can be seen that granular S powder, Co powder and graphene particles mix, and size is inhomogenous, not
It is fully compound.After tested, the maximum hydrogen storage capability for the composite hydrogen storage material that prepared by this experiment is 0.65wt%, and hydrogen storage ability is not
It is high.By contrast test 1 it is found that when low ball milling speed, S powder, Co powder and graphene are physical mixed state.
Contrast test 2：The ball grinder that is used in step 2 neutralization procedure four unlike this experiment and experiment 1 and abrading-ball
Material is stainless steel, other identical as experiment 1, obtains graphene composite hydrogen storage material.The stereoscan photograph of the material is such as
Shown in Fig. 8, from figure 8, it is seen that the ball grinder and grinding ball material quality due to stainless steel are softer, it cannot be fully broken by material
Broken, grinding, graphene and S powder, Co powder composite results are very uneven, and Product size is larger.The graphite that after tested prepared by this experiment
The maximum hydrogen storage capability of alkene composite hydrogen storage material be 0.82wt%, hydrogen storage ability is poor, contrast test 1 it is found that for ball grinder with
The material of abrading-ball has large effect to Compound Degree.
Experiment 2：The intercalation Co of this experiment1-xThe preparation method of the graphene-based composite material of S, according to the following steps into
Row：
One, it is 1 according to molar ratio by graphene and sulphur powder:1.2 are mixed, and mixed-powder I is obtained；
Two, ZrO is pressed2The mass ratio of abrading-ball and mixed-powder I is 18:1 ratio, by ZrO2Abrading-ball is packed into mixed-powder I
With ZrO2In the ball grinder of liner, it is filled with the high-purity argon gas that mass percentage concentration is 99.999%, finally fixes ball grinder
In ball mill, ball milling 30h under conditions of drum's speed of rotation is 1000rpm, to the end of ball milling, ball grinder is cooled to room temperature
Afterwards, graphene/S/ graphene powders are obtained；
Three, the molar ratio for pressing S and Co in graphene/S/ graphene powders is 1:0.9 graphene/the S/ for preparing step 2
Graphene powder is mixed with cobalt powder, obtains mixed-powder II；
Four, ZrO is pressed2The mass ratio of abrading-ball and mixed-powder II is 12:1, by ZrO2Abrading-ball is put into mixed-powder II to be had
ZrO2In the ball grinder of liner, it is filled with the high-purity argon gas that mass percentage concentration is 99.999%, ball grinder is finally fixed on ball
In grinding machine, ball milling 28h under conditions of drum's speed of rotation is 500rpm, to the end of ball milling, ball grinder is cooled to room temperature, and obtains layer
Between embedded Co1-xThe graphene-based composite material of S.
The intercalation Co that this experiment obtains1-xThe transmission electron microscope photo of the graphene-based composite material of S as shown in figure 9, from
Fig. 9 can be seen that intercalation Co1-xThe graphene-based composite material of S is sandwich structure, Co1-xS is embedded in the layer of graphene
Between, form graphene/Co1-xThe composite construction of S/ graphenes.
Intercalation Co prepared by this experiment1-xThe maximum hydrogen storage capability of the graphene-based composite material of S is 2.80wt%.
Cyclical stability test is carried out with 1 identical test method of experiment as shown in Figure 10, after recycling 20 times, this experiment
The intercalation Co of preparation1-xThe hydrogen storage ability of the graphene-based composite material of S remains at 80% or more.
With the intercalation Co for testing this experiment preparation with 1 identical test method of experiment1-xThe graphene-based composite wood of S
For material under the conditions of big discharge current density, high-rate discharge capacity is as shown in figure 11, learns, even if in the electric discharge of 1000mA/g
Under current density condition, discharge capability remains at 80% or more.
Claims (7)
1. a kind of intercalation Co1-xThe preparation method of the graphene-based composite material of S, it is characterised in that this method presses following step
It is rapid to carry out：
One, it is 1 according to molar ratio by graphene and sulphur powder:（1~1.5）It is mixed, obtains mixed-powder I；
Two, ZrO is pressed2The mass ratio of abrading-ball and mixed-powder I is（18~20）:1 ratio, by ZrO2Abrading-ball is filled with mixed-powder I
Enter with ZrO2In the ball grinder of liner, it is filled with high-purity argon gas, finally ball grinder is fixed in ball mill, in drum's speed of rotation
For 24 ~ 30h of ball milling under conditions of 900 ~ 1000rpm after ball grinder is cooled to room temperature, graphene/S/ stones are obtained to the end of ball milling
Black alkene powder；
Three, the molar ratio for pressing S and Co in graphene/S/ graphene powders is 1:（0.9~1）Graphene/S/ prepared by step 2
Graphene powder is mixed with cobalt powder, obtains mixed-powder II；
Four, ZrO is pressed2The mass ratio of abrading-ball and mixed-powder II is（10~15）:1, by ZrO2Abrading-ball is put into tool with mixed-powder II
There is ZrO2In the ball grinder of liner, it is filled with high-purity argon gas, finally ball grinder is fixed in ball mill, is in drum's speed of rotation
24 ~ 30h of ball milling under conditions of 400 ~ 500rpm, to the end of ball milling, ball grinder is cooled to room temperature, and obtains intercalation Co1-xS's
Graphene-based composite material；The composite material is by Co1-XS and the compound sandwich layer structure of graphene, Co1-xS is embedded in
Among the lamella of graphene, wherein graphene and Co1-XThe molar ratio of S is 1:（0.9~1.5）；Described in step 2 and step 4
High-purity argon gas refer to mass percentage concentration be more than 99.999% argon gas.
2. a kind of intercalation Co according to claim 11-xThe preparation method of the graphene-based composite material of S, feature
It is in step 1 that graphene and sulphur powder according to molar ratio are 1:1.2 mixing.
3. a kind of intercalation Co according to claim 11-xThe preparation method of the graphene-based composite material of S, feature
It is ZrO in step 22The mass ratio of abrading-ball and mixed-powder I is 19：1.
4. a kind of intercalation Co according to claim 11-xThe preparation method of the graphene-based composite material of S, feature
It is in step 2 that drum's speed of rotation is 950rpm, Ball-milling Time 28h.
5. a kind of intercalation Co according to claim 11-xThe preparation method of the graphene-based composite material of S, feature
It is that the molar ratio in step 3 by S and Co is 1:0.95 mixes sulphur powder with cobalt powder.
6. a kind of intercalation Co according to claim 11-xThe preparation method of the graphene-based composite material of S, feature
It is ZrO in step 42The mass ratio of abrading-ball and mixed-powder II is 12：1.
7. a kind of intercalation Co according to claim 11-xThe preparation method of the graphene-based composite material of S, feature
It is in step 4 that drum's speed of rotation is 450rpm, Ball-milling Time 28h.
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