CN109742379A - It is a kind of on Si/C composite material grow graphene method, utilize material made from this method and its application - Google Patents
It is a kind of on Si/C composite material grow graphene method, utilize material made from this method and its application Download PDFInfo
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- CN109742379A CN109742379A CN201910082486.0A CN201910082486A CN109742379A CN 109742379 A CN109742379 A CN 109742379A CN 201910082486 A CN201910082486 A CN 201910082486A CN 109742379 A CN109742379 A CN 109742379A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The present invention relates to a kind of to grow the method for graphene on Si/C composite material, utilize material made from this method and its application.This method comprises: (1) is sequentially depositing nickel film and copper film using chemical vapour deposition technique on Si/C compound, Cu/Ni/Si/C compound is obtained；(2) Cu/Ni/Si/C compound is placed in the environment of argon gas and hydrogen and is made annealing treatment；(3) it recycles chemical vapour deposition technique by treated that Cu/Ni/Si/C compound is placed under the atmosphere of methane and hydrogen reacts through step (2), then is cooled to room temperature under the protection of argon gas, to grow graphene on Si/C composite material.The addition in core material that the method reduce graphenes or the transfer to graphene film, coated technique can be avoided the chemical property for destroying existing graphene.
Description
Technical field
A kind of growing the present invention relates to technical field of graphene preparation more particularly on the Si/C composite material graphene
Method utilizes material made from this method and its application.
Background technique
Existing graphene battery is usually to add grapheme material on the basis of lithium battery, utilizes carbon dioxide gas handle
Graphene is made into the shape of puffed rice.The graphene of this puffed rice shape is referred to as " graphene ball ", these graphene balls
The surface for being covered on battery electrode is made into positive protective film and is used to improve charging rate, or using graphene as the addition material of battery core
Expect to improve the chemical property of original battery.
The existing coated graphite alkene film on lithium battery positive and negative electrode is firstly the need of graphene film is prepared, by what is prepared
Graphene film is shifted using chemical method, and the common polymer secondary transfer method in transfer process, this method can not
What is avoided brings pollution for graphene surface after the transfer, influences the chemical property of graphene itself, and transfering process is multiple
It is miscellaneous.
Present most of lithium ion batteries use graphite-like carbon as negative electrode material, though carbon negative pole material has many advantages, such as,
But its specific capacity is low, high-rate charge-discharge capability is poor；Silicon has highest specific capacity, but unit cell volume can be violent in cyclic process
Expansion generates " bulk effect ", and the stability of electrode structure is caused to be destroyed, under making it discharge capacity being rapid in cyclic process
Drop, though the shortcomings that Si/C composite material has neutralized silicium cathode material and carbon negative pole material, does not improve the charge and discharge times of battery
Rate.
Summary of the invention
The present invention prepares graphene on the basis of Si/C composite material, improves the rate of charge of original negative electrode material,
Reduce process.
To achieve the goals above, the present invention provides the following technical scheme that
1, a kind of method that graphene is grown on Si/C composite material, which comprises
(1) it is sequentially depositing nickel film and copper film on Si/C compound using chemical vapour deposition technique, obtains Cu/Ni/Si/C
Compound；
(2) Cu/Ni/Si/C compound is placed in the environment of argon gas and hydrogen and is made annealing treatment；
(3) recycle chemical vapour deposition technique will through step (2) treated Cu/Ni/Si/C compound is placed in methane and
It reacts under the atmosphere of hydrogen, then is cooled to room temperature under the protection of argon gas, to grow graphene on Si/C composite material.
2, method according to technical solution 1, in step (3), the flow of the methane is 200~300 standards milli
Liter/min, the flow of the hydrogen is 50~150 standard milliliters/minute.
3, the method according to technical solution 2, in step (3), the reaction carries out at 1000~1100 DEG C.
4, method according to technical solution 1, in step (2), the condition of the annealing are as follows:
First annealing stage: 900~950 DEG C of annealing temperature, annealing time 2~10 hours；With
Second annealing stage: 1000~1100 DEG C of annealing temperature, annealing time 20~30 hours.
5, method according to technical solution 1 utilizes the step of chemical vapor deposition nickel film in step (1)
Suddenly include:
Si/C compound is put into reaction chamber, is vacuumized, while being heated to the first reaction temperature；
It is passed through argon gas, then is passed through gaseous state carbonyl nickel deposition nickel film.
6, the method according to technical solution 5, first reaction temperature are 120~150 DEG C.
7, the method according to technical solution 5 utilizes the step of chemical vapor deposition copper film in step (1)
Suddenly include:
Continue to be passed through argon gas into reaction chamber, the second reaction temperature is heated under conditions of being continually fed into argon gas, simultaneously
It is passed through hydrogen and copper chloride vapor deposition copper film.
8, the method according to technical solution 7, second reaction temperature are 300~350 DEG C.
9, a kind of Si/C composite material with graphene, using the preparation of any one of technical solution 1 to 8 the method
At.
10, application of the Si/C composite material described in technical solution 9 with graphene in lithium cell cathode material.
Beneficial effect
Above-mentioned technical proposal of the invention has the advantages that
(1) compared with traditional graphene battery, reduce addition or to graphene thin of the graphene in core material
The transfer of film, coated technique can be avoided the chemical property for destroying existing graphene.
(2) preparation process is simple, and graphene is generated in Si/C composite substrate and is used as negative electrode material.
(3) chemical property for improving original lithium battery, improves the electric conductivity of rate of charge and battery.
Detailed description of the invention
Fig. 1 is the flow diagram of method provided by the invention.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution is clearly and completely described.Obviously, described embodiment is a part of the embodiments of the present invention, and
The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of on Si/C composite material grows the method for graphene, with reference to Fig. 1, the method packet
It includes:
(1) it is sequentially depositing nickel film and copper film on Si/C compound using chemical vapour deposition technique, obtains Cu/Ni/Si/C
Compound.
In some embodiments, include: using the step of chemical vapor deposition nickel film
Si/C compound is put into reaction chamber, is vacuumized, while being heated to the first reaction temperature, the first temperature is preferably
120~150 DEG C, for example, can be 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C；
It is passed through argon gas, then is passed through gaseous state carbonyl nickel deposition nickel film.
On this basis, can continue to deposit copper film as follows:
Continue to be passed through argon gas into reaction chamber, the second reaction temperature is heated under conditions of being continually fed into argon gas, simultaneously
It is passed through hydrogen and copper chloride vapor deposition copper film.Second temperature is preferably 300~350 DEG C, for example, can be 300 DEG C, 310
℃、320℃、330℃、340℃、350℃。
(2) Cu/Ni/Si/C compound is placed in the environment of argon gas and hydrogen and is made annealing treatment.The annealing
Condition it is preferred are as follows: the first annealing stage: 900~950 DEG C of annealing temperature is (for example, can be 900 DEG C, 910 DEG C, 920 DEG C, 930
DEG C, 940 DEG C, 950 DEG C), annealing time 2~10 hours (for example, can be 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7
Hour, 8 hours, 9 hours)；Second annealing stage: 1000~1100 DEG C of annealing temperature is (for example, can be 1000 DEG C, 1050
DEG C, 1100 DEG C), annealing time 20~30 hours (for example, can be 20 hours, 25 hours, 30 hours).
(3) recycle chemical vapour deposition technique will through step (2) treated Cu/Ni/Si/C compound is placed in methane and
It reacts under the atmosphere of hydrogen, then is cooled to room temperature under the protection of argon gas, to grow graphene on Si/C composite material.
Cu/Ni/Si/C compound is placed in H using chemical vapour deposition technique2/CH4In atmosphere, in this process, CH4It can occur point
Solution generates carbon atom and then is dissolved into metallic substrates, is finally cooled to room temperature sample under the protection of Ar.At high temperature, golden
Belonging to substrate has higher dissolubility to carbon atom, and with the reduction of temperature, the solubility of metal is also reduced, and is dissolved in metallic substrates
On carbon atom will be precipitated in metal surface to forming graphene.
In this step, the flow of the methane is preferably 200~300 standard milliliters/minute (for example, can be 200 marks
Quasi- ml/min, 210 standard milliliters/minute, 220 standard milliliters/minute, 230 standard milliliters/minute, 240 standard milliliters/point
Clock, 250 standard milliliters/minute, 260 standard milliliters/minute, 270 standard milliliters/minute, 280 standard milliliters/minute, 290 marks
Quasi- ml/min, 300 standard milliliters/minute), the flow of the hydrogen is preferably 50~150 standard milliliters/minute, for example,
It can be 50 standard milliliters/minute, 60 standard milliliters/minute, 70 standard milliliters/minute, 80 standard milliliters/minute, 90 standards
Ml/min, 100 standard milliliters/minute, 110 standard milliliters/minute, 120 standard milliliters/minute, 130 standard milliliters/point
Clock, 140 standard milliliters/minute, 150 standard milliliters/minute.Depositing temperature is preferably 1000~1100 DEG C, for example, can be
1000℃、1050℃、1100℃。
In Si/C compound, (Si/C compound can be according to existing method system using chemical vapour deposition technique by the present invention
It is standby) on deposit nickel film and copper film, it is advantageous to the growth of process for preparing graphenes by chemical vapour deposition film under the catalysis of copper and mickel,
Therefore the present invention continued growth graphene on the basis of preparation process.Principle are as follows: it is subsequent prepare graphene during,
Copper and mickel realizes the control to graphene number of plies.Growth of the graphene on copper surface follows surface from mechanism is limited, and may make copper
The graphene of upper growth is mostly based on single layer.When mixing the good nickel of molten carbon at copper-based bottom, can break copper from limitation behavior,
Grow the controllable graphene of the number of plies.That is, method provided by the invention can be on the basis for the method for preparing Si/C composite material
On prepare graphene, preparation process is simple, reduces coating or addition to grapheme material.
Inventor has found under study for action, also containing miscellaneous in the Cu/Ni/Si/C compound prepared under the catalysis of copper and mickel
The uneven surface of matter and the structure of the substance, to influence the growth of graphene.Based on this, the present invention is by the Cu/ of synthesis
Ni/Si/C compound is placed in Ar/H2Reducing atmosphere under made annealing treatment, (the organic and metal oxidation of the impurity of metal surface
Object) it can decompose or restore under high temperature, reducing atmosphere, evaporation, which occurs, for metal surface part atom should redeposit on metal
Surface keeps obtained surface more smooth, and impurity substantially reduces, and waviness becomes smaller, thus be conducive to the growth of graphene, into
And improve the quality and uniformity for growing graphene.
The present invention also provides a kind of Si/C composite material with graphene, the composite material is using provided by the invention
Method is prepared.This has the Si/C composite material of graphene to can be used as in negative electrode material in lithium battery.
It is the embodiment that the present invention enumerates below.
Embodiment 1
S1, it is sequentially depositing nickel film and copper film on Si/C compound using chemical vapour deposition technique, obtains Cu/Ni/Si/C
Compound.The step specifically includes:
Si/C compound is put into reaction chamber, is vacuumized, while being heated to 130 DEG C；
It is passed through argon gas, then is passed through gaseous state carbonyl nickel deposition nickel film.
After depositing nickel film, continues to be passed through argon gas into reaction chamber, 330 are heated under conditions of being continually fed into argon gas
DEG C, while being passed through hydrogen and copper chloride vapor deposition copper film.
S2, it Cu/Ni/Si/C compound is placed in the environment of argon gas and hydrogen makes annealing treatment.The annealing
Condition are as follows: the first annealing stage: 920 DEG C of annealing temperature, annealing time 5 hours；Second annealing stage: annealing temperature 1050
DEG C, annealing time 25 hours.
S3, by through S2, treated that Cu/Ni/Si/C compound is placed under the atmosphere of methane and hydrogen reacts, wherein methane
Flow be 250 standard milliliters/minute, the flow of hydrogen is 100 standard milliliters/minute, and the reaction time is 4 hours, then in argon
It is cooled to room temperature under the protection of gas, to grow graphene on Si/C composite material.
Embodiment 2
S1, it is sequentially depositing nickel film and copper film on Si/C compound using chemical vapour deposition technique, obtains Cu/Ni/Si/C
Compound.The step specifically includes:
Si/C compound is put into reaction chamber, is vacuumized, while being heated to 120 DEG C；
It is passed through argon gas, then is passed through gaseous state carbonyl nickel deposition nickel film.
After depositing nickel film, continues to be passed through argon gas into reaction chamber, 300 are heated under conditions of being continually fed into argon gas
DEG C, while being passed through hydrogen and copper chloride vapor deposition copper film.
S2, it Cu/Ni/Si/C compound is placed in the environment of argon gas and hydrogen makes annealing treatment.The annealing
Condition are as follows: the first annealing stage: 900 DEG C of annealing temperature, annealing time 10 hours；Second annealing stage: annealing temperature 1100
DEG C, annealing time 20 hours.
S3, by through S2, treated that Cu/Ni/Si/C compound is placed under the atmosphere of methane and hydrogen reacts, wherein methane
Flow be 200 standard milliliters/minute, the flow of hydrogen is 50 standard milliliters/minute, and the reaction time is 5 hours, then in argon gas
Protection under be cooled to room temperature, to grow graphene on Si/C composite material.
Embodiment 3
S1, it is sequentially depositing nickel film and copper film on Si/C compound using chemical vapour deposition technique, obtains Cu/Ni/Si/C
Compound.The step specifically includes:
Si/C compound is put into reaction chamber, is vacuumized, while being heated to 150 DEG C；
It is passed through argon gas, then is passed through gaseous state carbonyl nickel deposition nickel film.
After depositing nickel film, continues to be passed through argon gas into reaction chamber, 350 are heated under conditions of being continually fed into argon gas
DEG C, while being passed through hydrogen and copper chloride vapor deposition copper film.
S2, it Cu/Ni/Si/C compound is placed in the environment of argon gas and hydrogen makes annealing treatment.The annealing
Condition are as follows: the first annealing stage: 950 DEG C of annealing temperature, annealing time 2 hours；Second annealing stage: annealing temperature 1000
DEG C, annealing time 30 hours.
S3, by through S2, treated that Cu/Ni/Si/C compound is placed under the atmosphere of methane and hydrogen reacts, wherein methane
Flow be 300 standard milliliters/minute, the flow of hydrogen is 150 standard milliliters/minute, and the reaction time is 2 hours, then in argon
It is cooled to room temperature under the protection of gas, to grow graphene on Si/C composite material.
Utilize prior art preparation at lithium in the Si/C composite material for having graphene made from embodiment 1 to embodiment 3
Battery cathode.Through detecting, the rate of charge of battery and the electric conductivity of battery increase.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of method for growing graphene on Si/C composite material, which is characterized in that the described method includes:
(1) it is sequentially depositing nickel film and copper film on Si/C compound using chemical vapour deposition technique, it is compound obtains Cu/Ni/Si/C
Object；
(2) Cu/Ni/Si/C compound is placed in the environment of argon gas and hydrogen and is made annealing treatment；
(3) recycle chemical vapour deposition technique will through step (2) treated that Cu/Ni/Si/C compound is placed in methane and hydrogen
Atmosphere under react, then be cooled to room temperature under the protection of argon gas, to grow graphene on Si/C composite material.
2. the method according to claim 1, wherein the flow of the methane is 200~300 in step (3)
Standard milliliters/minute, the flow of the hydrogen are 50~150 standard milliliters/minute.
3. according to the method described in claim 2, it is characterized in that, the reaction is at 1000~1100 DEG C in step (3)
It carries out.
4. the method according to claim 1, wherein in step (2), the condition of the annealing are as follows:
First annealing stage: 900~950 DEG C of annealing temperature, annealing time 2~10 hours；With
Second annealing stage: 1000~1100 DEG C of annealing temperature, annealing time 20~30 hours.
5. the method according to claim 1, wherein utilizing chemical vapor deposition nickel in step (1)
The step of film includes:
Si/C compound is put into reaction chamber, is vacuumized, while being heated to the first reaction temperature；
It is passed through argon gas, then is passed through gaseous state carbonyl nickel deposition nickel film.
6. according to the method described in claim 5, it is characterized in that, first reaction temperature is 120~150 DEG C.
7. according to the method described in claim 5, it is characterized in that, utilizing chemical vapor deposition copper in step (1)
The step of film includes:
Continue to be passed through argon gas into reaction chamber, the second reaction temperature is heated under conditions of being continually fed into argon gas, is passed through simultaneously
Hydrogen and copper chloride vapor deposition copper film.
8. the method according to the description of claim 7 is characterized in that second reaction temperature is 300~350 DEG C.
9. a kind of Si/C composite material with graphene, which is characterized in that using any one of claim 1 to 8 the method
It is prepared.
10. application of the Si/C composite material as claimed in claim 9 with graphene in lithium cell cathode material.
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| CN112186363A (en) * | 2020-09-24 | 2021-01-05 | 武汉汉烯科技有限公司 | Flexible macroscopic graphene frequency selective surface |
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Application publication date: 20190510 |