CN106229493A - A kind of intercalation Co1 xgraphene-based composite of S and preparation method thereof - Google Patents
A kind of intercalation Co1 xgraphene-based composite of S and preparation method thereof Download PDFInfo
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Abstract
A kind of intercalation Co1‑xGraphene-based composite of S and preparation method thereof, it relates to graphene-based composite and preparation method thereof.It is intended to solve existing Co1‑xThe hydrogen storage property of S and graphene composite material is poor, the technical problem that performance is low and cyclical stability is poor under high intensity discharge electric current.The composite of the present invention is by Co1‑xThe sandwich layer structure that S and Graphene are combined, Co1‑xS is embedded in the middle of the lamella of Graphene, wherein Graphene and Co1‑XThe mol ratio of S is 1:(0.9～1.5).Preparation method: first Graphene is mixed with sulfur powder, ball milling, then add cobalt powder carry out mixing, ball milling, obtain intercalation Co1‑xThe graphene-based composite of S.This material is made its maximum hydrogen storage capability of hydrogen-bearing alloy electrode and is reached 3.73wt%, and the battery made, the hydrogen storage ability after circulating 50 times remains at more than 88%, can be used for hydrogen storage field.
Description
Technical field
The present invention relates to graphene-based composite and preparation method thereof.
Background technology
Hydrogen reserves in nature are the abundantest, have the highest energy matter ratio, cleanliness without any pollution, are expected to become following energy
A kind of main clean energy resource in source, but Hydrogen Energy is difficult to store, it is difficult to and using on a large scale, scientists is through long-term research
Find some material with carbon element, as hydrogen atom reversibly can be stored by activated carbon, CNT and Graphene etc. by electrochemical process
To wherein, the electrochemical hydrogen storage performance of the various different material with carbon element that metal hydride surface is modified has been carried out extensively by current people
General research.Wherein, Graphene is a kind of carbonaceous new material of carbon atom tightly packed one-tenth monolayer bi-dimensional cellular shape lattice structure,
There is high specific surface area, fabulous crystallinity and electric property, it is carried out surface and modifies available ideal answering
Close hydrogen storage material.In the modified metal material of numerous surfaces, Co base hydrogen storage system has excellent electrochemical hydrogen storage performance and relatively
High hydrogen storage capability receives the extensive concern of numerous scientific research personnel, shows through further investigation, Co based hydrogen storage material and non-gold
Belong to element S and form compound, for the effect of the raising played of hydrogen storage property.Cobalt sulphur compound comprises a series of atomic ratio
Compound, such as Co1-xS,CoS,CoS2,Co3S4,Co9S8Deng, wherein Co1-xS has because of its special deficient cobalt type structure well
Hydrogen storage prospect.Therefore, Co is utilized1-xThe grapheme modified surface of S, it will be greatly improved hydrogen storage property.Obtain preferable surface to modify
Effect, should be not only therebetween the mixing of physics, and should have chemistry key and, and Co1-xThe S modification area to Graphene
The biggest, effect is the best, but current complex method is all by granular Co1-xS is multiple with the graphenic surface physics of multiple structure
Close, granular Co1-xS is scattered in multi-layer graphene surface, Co equably1-xS is the highest to graphenic surface degree of modification, it is impossible to
Accomplishing that the graphenic surface to each layer all carries out large-area chemical modification, utilizing the compound of this type to carry out hydrogen storage should
With, its hydrogen storage property is undesirable, and the performance under high intensity discharge electric current is relatively low and cyclical stability is the most poor.
Summary of the invention
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 of S and
Its preparation method.
The intercalation Co of the present invention1-xThe graphene-based composite of S is by Co1-xThe sandwich that S and Graphene are combined
Layer structure, Co1-xS is embedded in the middle of the lamella of Graphene, wherein Graphene and Co1-XThe mol ratio of S is 1:(0.9～1.5).
Above-mentioned intercalation Co1-xThe preparation method of the graphene-based composite of S, sequentially includes the following steps:
One, it is 1:(1～1.5 with sulfur powder according to mol ratio by Graphene) mix, obtain mixed-powder I；
Two, by ZrO2Abrading-ball is (18～20) with the mass ratio of mixed-powder I: the ratio of 1, by ZrO2Abrading-ball and mixed powder
End I loading has ZrO2In the ball grinder of liner, it is filled with high-purity argon gas, finally ball grinder is fixed in ball mill, at ball milling
Machine rotating speed is ball milling 24～30h under conditions of 900～1000rpm, treats that ball milling terminates, after ball grinder is cooled to room temperature, obtains stone
Ink alkene/S/ graphene powder；
Three, it is 1:(0.9～1 by the mol ratio of S Yu Co in Graphene/S/ graphene powder) graphite prepared by step 2
Alkene/S/ graphene powder mixes with cobalt powder, obtains mixed-powder II；
Four, by ZrO2Abrading-ball is (10～15) with the mass ratio of mixed-powder II: 1, by ZrO2Abrading-ball is put with mixed-powder II
Enter 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
Being ball milling 24～30h under conditions of 400～500rpm, treat that ball milling terminates, ball grinder is cooled to room temperature, obtains intercalation Co1- xThe graphene-based composite of S.
The present invention uses high-energy ball milling method, higher rotating speed to allow the material to carry out being fully contacted, act on and reacting,
Under high speed conditions, first with Graphene and S as raw material, abrading-ball at a high speed makes internal energy drastically raise, first in mechanical milling process
The sulfur granules first making powder melts, and liquid sulfur is attached to graphene sheet layer surface, and from the edge of Graphene or fault location
Penetrate into interlayer, obtain Graphene/S/ Graphene sandwich structure composite, continue this composite is carried out high-energy ball milling,
Making part sulfur and the further chemical combination of active carbon atom in Graphene of interlayer, generate S-C key, the generation of chemical bond is conducive to
Stable and the transmission of electronics of structure.It is further continued for utilizing high-energy ball milling to mix Co powder, can make by controlling ratio of grinding media to material and rotating speed
Obtain S Yu the Co chemical combination between the graphene layer in Graphene/S/ graphene composite material and generate Co1-xS, obtains Graphene/Co1-xS/
Graphene sandwich structure composite hydrogen storage material.This Co1-xS embeds face the biggest to single-layer graphene surface between graphene layer
The long-pending material modified is by producing chemical bond and by the particle of the reversible transmission of chemical bond between interface so that the hydrogen storage property of material
It is greatly improved.This composite hydrogen storage material can prepare hydrogen-bearing alloy electrode, is applied in Ni-MH battery equal energy source system, maximum storage
Hydrogen capacity is up to 3.73wt%, electrochemical hydrogen storage excellent performance.Intercalation Co1-xThe graphene-based composite of S is prepared as electricity
Pond, after circulation 50 times, intercalation Co1-xThe hydrogen storage ability of the graphene-based composite of S remains at more than 88%.With
Time under the conditions of the discharge current density of 1000mA/g, its discharge capability remains at more than 80%.Can be used for hydrogen storage field.This
The preparation technology of invention is simple, and safety is high.
Accompanying drawing explanation
Fig. 1 is the intercalation Co of test 1 preparation1-xThe transmission electron microscope photo of the graphene-based composite of S；
Fig. 2 is the intercalation Co of test 1 preparation1-xThe XRD spectra of the graphene-based composite of S；
Fig. 3 is the intercalation Co of test 1 preparation1-xThe XPS-C test result of the graphene-based composite of S；
Fig. 4 is the intercalation Co of test 1 preparation1-xThe XPS-S test result of the graphene-based composite of S；
Fig. 5 is the intercalation Co of test 1 preparation1-xThe stable circulation linearity curve of the graphene-based composite of S；
Fig. 6 is the intercalation Co of test 1 preparation1-xThe high-rate discharge ability curve of the graphene-based composite of S；
Fig. 7 is the stereoscan photograph of the Graphene composite hydrogen storage material of contrast test 1 preparation；
Fig. 8 is the stereoscan photograph of the Graphene composite hydrogen storage material of contrast test 2 preparation；
Fig. 9 is the intercalation Co of test 2 preparation1-xThe transmission electron microscope photo of the graphene-based composite of S；
Figure 10 is the intercalation Co of test 2 preparation1-xThe stable circulation linearity curve of the graphene-based composite of S；
Figure 11 is the intercalation Co of test 2 preparation1-xThe high-rate discharge ability curve of the graphene-based composite of S；
Detailed description of the invention
Detailed description of the invention one: the intercalation Co of present embodiment1-xThe graphene-based composite of S is by Co1-xS and
The sandwich layer structure that Graphene is compound, Co1-xS is embedded in the middle of the lamella of Graphene, wherein Graphene and Co1-XS rubs
That ratio is 1:(0.9～1.5).
Detailed description of the invention two: preparation intercalation Co described in detailed description of the invention one1-xThe graphene-based composite wood of S
The preparation method of material, sequentially includes the following steps:
One, it is 1:(1～1.5 with sulfur powder according to mol ratio by Graphene) mix, obtain mixed-powder I；
Two, by ZrO2Abrading-ball is (18～20) with the mass ratio of mixed-powder I: the ratio of 1, by ZrO2Abrading-ball and mixed powder
End I loading has ZrO2In the ball grinder of liner, it is filled with high-purity argon gas, finally ball grinder is fixed in ball mill, at ball milling
Machine rotating speed is ball milling 24～30h under conditions of 900～1000rpm, treats that ball milling terminates, after ball grinder is cooled to room temperature, obtains stone
Ink alkene/S/ graphene powder；
Three, it is 1:(0.9～1 by the mol ratio of S Yu Co in Graphene/S/ graphene powder) graphite prepared by step 2
Alkene/S/ graphene powder mixes with cobalt powder, obtains mixed-powder II；
Four, by ZrO2Abrading-ball is (10～15) with the mass ratio of mixed-powder II: 1, by ZrO2Abrading-ball is put with mixed-powder II
Enter 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
Being ball milling 24～30h under conditions of 400～500rpm, treat that ball milling terminates, ball grinder is cooled to room temperature, obtains intercalation Co1- xThe graphene-based composite of S.
Detailed description of the invention three: present embodiment is the height described in step 2 and four unlike detailed description of the invention two
Pure argon refers to the argon that mass percentage concentration is more than 99.999%.Other is identical with detailed description of the invention two.
Detailed description of the invention four: in present embodiment step one unlike detailed description of the invention two or three Graphene with
Sulfur powder is 1:1.2 mixing according to mol ratio.Other is identical with detailed description of the invention two or three.
Detailed description of the invention five: ZrO in present embodiment step 2 unlike one of detailed description of the invention two to four2
Abrading-ball is 19:1 with the mass ratio of mixed-powder I.Other is identical with one of detailed description of the invention two to four.
Detailed description of the invention six: ball milling in present embodiment step 2 unlike one of detailed description of the invention two to five
Machine rotating speed is 950rpm, and Ball-milling Time is 28h.Other is identical with one of detailed description of the invention two to five.
Detailed description of the invention seven: present embodiment presses S in step 3 unlike one of detailed description of the invention two to six
It is that sulfur powder is mixed by 1:0.95 with cobalt powder with the mol ratio of Co.Other is identical with one of detailed description of the invention two to six.
Detailed description of the invention eight: ZrO in present embodiment step 4 unlike one of detailed description of the invention two to seven2
Abrading-ball is 12:1 with the mass ratio of mixed-powder II.Other is identical with one of detailed description of the invention two to seven.
Detailed description of the invention nine: ball milling in present embodiment step 4 unlike one of detailed description of the invention two to seven
Machine rotating speed is 450rpm, and Ball-milling Time is 28h.Other is identical with one of detailed description of the invention two to seven.
By following verification experimental verification beneficial effects of the present invention:
Test 1: the intercalation Co of this test1-xThe preparation method of the graphene-based composite of S, enters according to the following steps
OK:
One, it is that 1:1 mix with sulfur powder according to mol ratio by Graphene, obtains mixed-powder I；
Two, by ZrO2Abrading-ball and the ratio that mass ratio is 20:1 of mixed-powder I, by ZrO2Abrading-ball loads with mixed-powder I
There is ZrO2In the ball grinder of liner, it is filled with the high-purity argon gas that mass percentage concentration is 99.999%, finally ball grinder is fixed
In ball mill, ball milling 24h under conditions of drum's speed of rotation is 900rpm, treat that ball milling terminates, after ball grinder is cooled to room temperature,
Obtain Graphene/S/ graphene powder；
Three, it is 1:(0.9～1 by the mol ratio of S Yu Co in Graphene/S/ graphene powder) graphite prepared by step 2
Alkene/S/ graphene powder mixes with cobalt powder, obtains mixed-powder II；
Four, by ZrO2Abrading-ball is 15:1 with the mass ratio of mixed-powder II, 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%, finally ball grinder is fixed on ball
In grinding machine, ball milling 24h under conditions of drum's speed of rotation is 450rpm, treat that ball milling terminates, ball grinder is cooled to room temperature, obtains layer
Between embed Co1-xThe graphene-based composite of S.
The intercalation Co that this test obtains1-xThe transmission electron microscope photo of the graphene-based composite of S as it is shown in figure 1, from
Fig. 1 it can be seen that composite is sandwich layer structure, Co1-xS is embedded in the middle of graphene sheet layer, wherein Graphene with
Co1-xThe mol ratio of S is 1:1.This photo can be seen that without single Co1-xS granule and Sheet Graphite alkene exist, Co1-xS
With Graphene under high-energy ball milling effect, it is complex as a whole.
Fig. 2 is the intercalation Co that test 1 obtains1-xThe XRD spectra of the graphene-based composite of S, can from Fig. 2
Going out, composite is by Co1-xS and Graphene composition.
Fig. 3 is the intercalation Co of this test preparation1-xThe graphene-based composite of S XPS C element analysis test
As a result, compared with original rGO, the material after being combined shows typical C-S characteristic peak (285.6eV), and this illustrates Co1-xIn S
S element and rGO in C element there occurs chemical action, create chemical bond.
Fig. 4 is the intercalation Co of this test preparation1-xThe XPS S elementary analysis test knot of the graphene-based composite of S
Really, with simple Co1-xS-phase ratio, the material after being combined shows that typical S-C characteristic peak (163.6eV) also illustrates Co1-xS pair
RGO modifies successfully on surface.
The maximum hydrogen storage capability of the composite hydrogen storage material that this test obtains is 2.83wt%, electrochemical hydrogen storage excellent performance.
The intercalation Co of this test preparation1-xThe method of the cyclical stability test of the graphene-based composite of S is such as
Under:
(1) preparation of positive pole: first by powder Ni (OH)2It is ground mixing all according to the mass ratio of 8:1 with Co powder
Even, it is subsequently adding the politef (PTFE) of appropriate liquid state.The pressure compacting of nickel foam 50MPa finally painting wiped
Become electrode, under room temperature, i.e. obtain anode after drying.
(2) preparation of negative pole: by intercalation Co1-xThe graphene-based composite of S and acetylene black are according to the quality of 7:2
After more uniform than ground and mixed in mortar, the politef adding liquid state is uniformly coated onto in nickel foam, same 50MPa's
Pressure electrode pressing, treats the most dried the battery cathode.
(3) electrolyte is the high concentration KOH solution of 6mol/L.
(4) battery test system step is set: first arranges in electrode immerses electrolyte and stands 3min.Then with 100mA/
The density of charging current of g is charged 10h to electrode material, stands 2min before discharge with steady potential after charging complete,
It is discharged to 0V again, the charge and discharge process being so circulated under the discharge current density of 30mA/g.Finally take advantage of with discharge current
Characterize total discharge capacity of electrode, unit total time again divided by the numerical value obtained by the consumption of active material on electrode with electric discharge
For mAh/g.
The relation curve of the cycle-index that cyclical stability test process obtains and hydrogen storage ability is as it is shown in figure 5, can from Fig. 5
To find out, after circulating 20 times, intercalation Co1-xThe hydrogen storage ability of the graphene-based composite of S remains at more than 80%.
Test the intercalation Co of this test preparation1-xThe graphene-based composite of S is in big discharge current density condition
Under, its high-rate discharge capacity, the discharge current density obtained and high-rate discharge capacity graph of relation as shown in Figure 6, from
Even if Fig. 6 is it can be seen that under the conditions of the discharge current density of 1000mA/g, its discharge capability remains at more than 80%.
Contrast test 1: the drum's speed of rotation in this test step 2 and step 4 unlike test 1 is set as
300rpm, other is the most identical with test 1, Graphene composite hydrogen storage material that is that obtain.The scanning electron microscope of this composite hydrogen storage material shines
Sheet is not as it is shown in fig. 7, from figure 7 it can be seen that granular S powder, Co powder and Graphene confusion, size heterogeneity, have
The most compound.After tested, the maximum hydrogen storage capability of the composite hydrogen storage material of this test preparation is 0.65wt%, and hydrogen storage ability is not
High.From contrast test 1, when ball milling speed is low, S powder, Co powder and Graphene are physical mixed state.
Contrast test 2: the ball grinder that this test uses in step 2 neutralization procedure four unlike test 1 and abrading-ball
Material is rustless steel, and other is all identical with test 1, obtains Graphene composite hydrogen storage material.The stereoscan photograph of this material is such as
Shown in Fig. 8, from figure 8, it is seen that owing to stainless ball grinder is softer with grinding ball material quality, it is impossible to material is the most broken
Broken, grind, Graphene and S powder, that Co powder is combined result is the most uneven, and Product size is bigger.The graphite of this test preparation after tested
The maximum hydrogen storage capability of alkene composite hydrogen storage material is 0.82wt%, and hydrogen storage ability is poor, and contrast test 1 understands, for ball grinder with
The material of abrading-ball has large effect to Compound Degree.
Test 2: the intercalation Co of this test1-xThe preparation method of the graphene-based composite of S, enters according to the following steps
OK:
One, it is that 1:1.2 mix with sulfur powder according to mol ratio by Graphene, obtains mixed-powder I；
Two, by ZrO2Abrading-ball and the ratio that mass ratio is 18:1 of mixed-powder I, by ZrO2Abrading-ball loads with mixed-powder I
There is ZrO2In the ball grinder of liner, it is filled with the high-purity argon gas that mass percentage concentration is 99.999%, finally ball grinder is fixed
In ball mill, ball milling 30h under conditions of drum's speed of rotation is 1000rpm, treat that ball milling terminates, ball grinder is cooled to room temperature
After, obtain Graphene/S/ graphene powder；
Three, it is Graphene/S/ that step 2 is prepared by 1:0.9 by the mol ratio of S Yu Co in Graphene/S/ graphene powder
Graphene powder mixes with cobalt powder, obtains mixed-powder II；
Four, by ZrO2Abrading-ball is 12:1 with the mass ratio of mixed-powder II, 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%, finally ball grinder is fixed on ball
In grinding machine, ball milling 28h under conditions of drum's speed of rotation is 500rpm, treat that ball milling terminates, ball grinder is cooled to room temperature, obtains layer
Between embed Co1-xThe graphene-based composite of S.
The intercalation Co that this test obtains1-xThe transmission electron microscope photo of the graphene-based composite of S as it is shown in figure 9, from
Fig. 9 is it can be seen that intercalation Co1-xThe graphene-based composite of S is sandwich structure, Co1-xS embeds the layer of Graphene
Between, form Graphene/Co1-xThe composite construction of S/ Graphene.
The intercalation Co of this test preparation1-xThe maximum hydrogen storage capability of the graphene-based composite of S is 2.80wt%.
It is circulated stability test as shown in Figure 10 with test 1 identical method of testing, after circulating 20 times, this test
The intercalation Co of preparation1-xThe hydrogen storage ability of the graphene-based composite of S remains at more than 80%.
Intercalation Co prepared by this test is tested with test 1 identical method of testing1-xThe graphene-based composite wood of S
Material is under the conditions of big discharge current density, and its high-rate discharge capacity as shown in figure 11, is learnt, even if in the electric discharge of 1000mA/g
Under current density condition, its discharge capability remains at more than 80%.
Claims (9)
1. an intercalation Co1-xThe graphene-based composite of S, it is characterised in that this composite is by Co1-XS and stone
The sandwich layer structure that ink alkene is compound, Co1-xS is embedded in the middle of the lamella of Graphene, wherein Graphene and Co1-XS mole
Ratio is 1:(0.9～1.5).
2. the preparation a kind of intercalation Co described in claim 11-xThe method of the graphene-based composite of S, it is characterised in that
The method sequentially includes the following steps:
One, it is 1:(1～1.5 with sulfur powder according to mol ratio by Graphene) mix, obtain mixed-powder I；
Two, by ZrO2Abrading-ball is (18～20) with the mass ratio of mixed-powder I: the ratio of 1, by ZrO2Abrading-ball fills with mixed-powder I
Enter 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
It is ball milling 24～30h under conditions of 900～1000rpm, treats that ball milling terminates, after ball grinder is cooled to room temperature, obtain Graphene/S/
Graphene powder；
Three, it is 1:(0.9～1 by the mol ratio of S Yu Co in Graphene/S/ graphene powder) Graphene prepared by step 2/
S/ graphene powder mixes with cobalt powder, obtains mixed-powder II；
Four, by ZrO2Abrading-ball is (10～15) with the mass ratio of mixed-powder II: 1, by ZrO2Abrading-ball and mixed-powder II put into tool
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 24～30h under conditions of 400～500rpm, treat that ball milling terminates, and ball grinder is cooled to room temperature, obtain intercalation Co1-xS
Graphene-based composite.
A kind of intercalation Co the most according to claim 21-xThe preparation method of the graphene-based composite of S, its feature
It is that the high-purity argon gas described in step 2 and four refers to the argon that mass percentage concentration is more than 99.999%.
4. according to a kind of intercalation Co described in Claims 2 or 31-xThe preparation method of the graphene-based composite of S, its
It is characterised by step one that Graphene is that 1:1.2 mixes with sulfur powder according to mol ratio.
5. according to a kind of intercalation Co described in Claims 2 or 31-xThe preparation method of the graphene-based composite of S, its
It is characterised by ZrO in step 22Abrading-ball is 19:1 with the mass ratio of mixed-powder I.
6. according to a kind of intercalation Co described in Claims 2 or 31-xThe preparation method of the graphene-based composite of S, its
Being characterised by step 2 that drum's speed of rotation is 950rpm, Ball-milling Time is 28h.
7. according to a kind of intercalation Co described in Claims 2 or 31-xThe preparation method of the graphene-based composite of S, its
It is characterised by step 3 by the mol ratio of S with Co being that sulfur powder is mixed by 1:0.95 with cobalt powder.
8. according to a kind of intercalation Co described in Claims 2 or 31-xThe preparation method of the graphene-based composite of S, its
It is characterised by ZrO in step 42Abrading-ball is 12:1 with the mass ratio of mixed-powder II.
9. according to a kind of intercalation Co described in Claims 2 or 31-xThe preparation method of the graphene-based composite of S, its
Being characterised by step 4 that drum's speed of rotation is 450rpm, Ball-milling Time is 28h.
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| RAJENDRAN RAMACHANDRAN ET AL.: "Co9S8 nanoflakes on graphene (Co9S8/G nanocomposities for high performance supercapacitors", 《RSC ADVANCES》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111073499A (en) * | 2019-12-27 | 2020-04-28 | 哈尔滨工业大学 | Preparation method of red flag mark for deep space detector |
| CN111073499B (en) * | 2019-12-27 | 2021-06-15 | 哈尔滨工业大学 | Preparation method of red flag mark for deep space detector |
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| CN106229493B (en) | 2018-08-17 |
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