CN116936786A - Preparation method of graphene modified aluminum foil - Google Patents
Preparation method of graphene modified aluminum foil Download PDFInfo
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- CN116936786A CN116936786A CN202210362225.6A CN202210362225A CN116936786A CN 116936786 A CN116936786 A CN 116936786A CN 202210362225 A CN202210362225 A CN 202210362225A CN 116936786 A CN116936786 A CN 116936786A
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- 239000011888 foil Substances 0.000 title claims abstract description 100
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- -1 graphene modified aluminum Chemical class 0.000 title abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000010410 layer Substances 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000007797 corrosion Effects 0.000 claims abstract description 16
- 238000005260 corrosion Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 239000002344 surface layer Substances 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000000197 pyrolysis Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000003892 spreading Methods 0.000 claims description 2
- 230000007480 spreading Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000007740 vapor deposition Methods 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 8
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 6
- 229910039444 MoC Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of graphene modified aluminum foil, which comprises the steps of placing the aluminum foil into treatment fluid, enabling an aluminum oxide layer on the surface of the aluminum foil to perform corrosion reaction with the treatment fluid, controlling reaction time, enabling aluminum oxide on the surface layer to react and dissolve, and forming a rough surface structure; by controlling the kind and the reaction time of the treatment liquid, the aluminum oxide layer is not completely corroded and dissolved while the rough structure is formed on the surface of the aluminum foil. When graphene is grown by subsequent vapor deposition, the cracked carbon is easy to form a C-O-Al covalent bond with oxygen in alumina, and the C-O-Al covalent bond remarkably improves the interfacial adhesion between the graphene layer and the aluminum foil and improves the peeling strength of the graphene layer.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a preparation method of graphene modified aluminum foil.
Background
Aluminum foil is widely used as a material of a positive electrode current collector in lithium ion batteries due to its excellent mechanical strength and ductility, low price, and usability such as light weight and high conductivity.
The aluminum foil used for the positive electrode of the lithium ion battery at present is mainly photo foil, corrosion aluminum foil and coating aluminum foil. The smooth surface of the optical foil has limited contact area with the positive electrode material, so that the problems of high interface resistance, separation of the positive electrode material and the aluminum foil and the like are easily caused, and the performance of the battery is influenced.
Although the specific surface area of the aluminum foil can be obviously increased by corroding the surface of the aluminum foil, the corrosion process is often complex, the corrosion solution and the added current are needed to assist, the aluminum oxide passivation layer on the surface of the aluminum foil is also needed to be broken down, the process is complex, and the mechanical strength of the aluminum foil is easy to be reduced. CN109609997a discloses a method for preparing an etched aluminum foil, which comprises placing the aluminum foil in an electrolyte, applying alternating current to perform hole distribution etching, and breaking down a passivation film on the surface of the aluminum foil to perform deeper etching.
CN113422065a discloses a preparation method of a molybdenum carbide coating aluminum foil, wherein molybdenum carbide has excellent conductivity and is used for improving the conductivity of the coating aluminum foil, while a molybdenum carbide coating is adhered to the surface of the aluminum foil mainly by using polyacrylonitrile as a binder, and the polyacrylonitrile is used as a high polymer material, so that the conductivity of the molybdenum carbide coating is obviously lower than that of the molybdenum carbide coating, and the conductivity of the molybdenum carbide coating is obviously reduced. Graphene is considered as a star material in the 21 st century, has a unique two-dimensional atomic crystal with a honeycomb structure, shows excellent mechanical, thermal, optical, electrical and other properties, has ultrahigh electron mobility and lowest resistivity at normal temperature, is the material with the lowest resistivity in the world at present, and has important application prospects in various fields such as materials, energy sources and the like.
The preparation method of the Plasma Enhanced Chemical Vapor Deposition (PECVD) is a method for preparing the graphene with the three-dimensional structure by adopting a radio frequency plasma body to assist in chemical vapor deposition reaction, and can realize long-time continuous growth of raw materials by combining a roll-to-roll technology. The method utilizes plasma to effectively crack precursor molecules, reduces chemical reaction potential barrier, and enables the whole reaction system to realize film forming reaction at a lower temperature.
Therefore, a method for improving the conductivity of the surface coating of the aluminum foil and improving the interfacial adhesion between the coating and the aluminum foil is needed, and has important significance for improving the performance of the lithium ion battery.
Disclosure of Invention
Aiming at the defects of the prior art, the preparation method of the high-peel strength graphene layer modified aluminum foil provided by the invention can obviously improve the conductivity of the graphene layer, and simultaneously improve the interfacial adhesion between the graphene layer and the aluminum foil and the peel strength of the graphene layer. The preparation method is simple and is suitable for large-scale production.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a graphene layer modified aluminum foil with high peel strength, which specifically comprises the following steps:
s1, placing an aluminum foil into a treatment liquid, enabling an aluminum oxide layer on the surface of the aluminum foil to perform corrosion reaction with the treatment liquid, controlling the reaction time, and enabling the aluminum oxide on the surface layer to react and dissolve to form a rough surface structure;
s2, cleaning the corroded aluminum foil with deionized water, drying, spreading and placing in a heating area of a PECVD (plasma chemical vapor deposition) tubular atmosphere furnace, and introducing non-oxidizing gas to thoroughly clean and remove air in a furnace chamber;
s3, vacuumizing the furnace chamber, and then introducing a carbon source and non-oxidizing gas to enable the furnace chamber to generate certain air pressure, wherein the non-oxidizing gas is carrier gas of the carbon source, and conveying the carbon source to a heating area of the PECVD tubular atmosphere furnace;
and S4, starting plasma, heating to the growth temperature of plasma chemical vapor deposition, preserving heat for 10 min-3 h, depositing carbon source molecules on the surface of the aluminum foil through pyrolysis, growing to form graphene, and cooling to obtain the graphene-modified aluminum foil.
According to one embodiment of the present invention, the treatment liquid is one or more of phosphoric acid, nitrous acid, and oxalic acid. Compared with the technical means of adopting strong acid as the corrosive liquid or adding current assistance, the method adopts phosphoric acid, nitrous acid or oxalic acid as the treatment liquid, has milder conditions and more controllable operation, and can lead the cracked carbon to easily form a C-O-Al covalent bond with oxygen in alumina when the graphene grows by subsequent vapor deposition, so that the C-O-Al covalent bond can obviously improve the interfacial adhesion between the graphene layer and the aluminum foil and improve the peeling strength of the graphene layer.
According to an embodiment of the present invention, in step S1, the reaction time is controlled to be 20S-3min and the reaction temperature is controlled to be 40-70 ℃.
According to an embodiment of the present invention, the graphene layer modified aluminum foil contains a c—o—al covalent bond.
According to an embodiment of the present invention, the thickness of the aluminum foil is 10 to 50 μm.
According to an embodiment of the present invention, in the step S2, the drying temperature is 50-100 ℃ and the drying time is 10 min-5 h.
According to an embodiment of the present invention, in step S2, the non-oxidizing gas is one or more of argon, helium or nitrogen.
According to an embodiment of the present invention, the carbon source gas is selected from one or more of methane, ethane and acetylene.
According to an embodiment of the present invention, the flow rate of the carbon source gas is 0.02sccm to 50sccm; the percentage of the carbon source to the total volume of the carbon source and the non-oxidizing gas may be 0.1% to 100%.
According to an embodiment of the present invention, in the step S3, the gas pressure after the carbon source and the non-oxidizing gas are introduced is 2Pa to 100Pa.
According to an embodiment of the present invention, in step S4, the growth temperature of the plasma chemical vapor deposition is 400 ℃ to 700 ℃, and the temperature rising rate is 1 ℃/min to 50 ℃/min.
According to an embodiment of the present invention, the plasma source is a radio frequency plasma, a microwave plasma or a direct current high voltage plasma, and the radio frequency power is 10W to 1000W.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
1. the aluminum foil surface is easy to oxidize in the air to form an aluminum oxide layer, and the original smooth aluminum oxide layer surface can form a coarse structure through corrosion of treatment fluid, so that the specific surface area of the aluminum foil is improved, and the contact area of the aluminum foil and the graphene layer can be remarkably improved and the peeling strength of the graphene layer can be improved during subsequent vapor deposition growth of graphene.
2. Compared with the traditional aluminum foil corrosion method that the aluminum oxide layer is required to be broken down and thoroughly corroded, the aluminum foil corrosion method adopts phosphoric acid or nitrous acid or oxalic acid as the corrosive liquid, and can ensure that the aluminum oxide layer is not completely corroded and dissolved while the rough structure is formed on the surface of the aluminum foil by controlling the corrosion time. Therefore, when graphene is grown by subsequent vapor deposition, the cracked carbon is easy to form a C-O-Al covalent bond with oxygen in alumina, and the C-O-Al covalent bond remarkably improves the interfacial adhesion between the graphene layer and the aluminum foil and improves the peeling strength of the graphene layer.
3. After the surface of the graphene-modified aluminum foil is coated with the positive electrode material of the lithium ion battery, the interface resistance of the aluminum foil and the positive electrode material can be obviously reduced, and the charge-discharge capacity, the rate capability and the cycle stability of the battery are improved. The graphene modified aluminum foil prepared by the method has low cost, and the synthesis method is simple and effective and is suitable for large-scale production.
Drawings
Fig. 1 is a schematic diagram of a preparation flow of a graphene-modified aluminum foil according to the present invention.
FIG. 2 is a scanning electron micrograph of the aluminum foil of example 1 before corrosion.
FIG. 3 is a scanning electron micrograph of the aluminum foil of example 1 after corrosion.
Fig. 4 is a scanning electron micrograph of the graphene-modified aluminum foil of example 1.
Fig. 5 is an X-ray photoelectron spectrum C1s of the graphene-modified aluminum foil of example 1.
Fig. 6 is a schematic structural diagram of the graphene-modified aluminum foil in example 1.
Detailed Description
In order to make the above features and advantages of the present invention more comprehensible, embodiments accompanied with figures are described in detail below.
Example 1
The embodiment provides a preparation method of a graphene layer modified aluminum foil with high peel strength, which comprises the following steps:
1. and (3) putting the aluminum foil with the thickness of 10 mu m into phosphoric acid, soaking for 20s at the temperature of 40 ℃ to enable part of the aluminum oxide layer on the surface of the aluminum foil to react with the phosphoric acid in a corrosion way, so that a rough surface structure is formed.
2. Repeatedly cleaning the corroded aluminum foil with deionized water, removing phosphoric acid remained on the surface, and drying at 50 ℃ for 10min. And (3) flatly laying the dried aluminum foil, putting the aluminum foil into a heating area of a PECVD tubular atmosphere furnace, and introducing argon to thoroughly clean and remove air in the furnace chamber. And vacuumizing the furnace chamber, and then introducing methane and argon, wherein the flow rate of the methane is 0.02sccm, the flow rate of the argon is 20sccm, and the furnace chamber generates certain air pressure, and the air pressure is controlled within the range of 2 Pa-100 Pa. And starting radio frequency plasma with the power of 10W, heating to 400 ℃ at the speed of 1 ℃/min, preserving heat for 10min, depositing carbon source molecules on the surface of the aluminum foil through pyrolysis, growing to form graphene, and cooling to obtain the graphene-modified aluminum foil.
The scanning electron microscope photograph before the aluminum foil is corroded is shown in fig. 2, and the aluminum foil surface before the corrosion is relatively smooth. The scanning electron microscope photograph of the etched aluminum foil is shown in fig. 3, and it can be seen that the surface of the etched aluminum foil is rough, but the perforated structure like a conventional etched aluminum foil is not formed. The scanning electron microscope photograph of the aluminum foil modified by the graphene is shown in fig. 4, and a uniform lamellar graphene layer is formed on the surface of the corroded aluminum foil. The C1s spectrum of the X-ray photoelectron spectrum of the sample is shown in FIG. 5, and C-O bonds appear, which proves that carbon in graphene can actually react with an aluminum oxide layer on the surface of the aluminum foil, and is beneficial to improving the interfacial adhesion between the graphene layer and the aluminum foil. The structural schematic diagram of the graphene-modified aluminum foil is shown in fig. 6, and the aluminum foil comprises a metal aluminum layer, an aluminum oxide layer and a graphene layer.
Example 2
The embodiment provides a preparation method of a graphene layer modified aluminum foil with high peel strength, which comprises the following steps:
1. and (3) putting the aluminum foil with the thickness of 50 mu m into nitrous acid, and soaking for 3min at the temperature of 70 ℃ to enable part of the aluminum oxide layer on the surface of the aluminum foil to perform corrosion reaction with the nitrous acid to form a rough surface structure.
2. Repeatedly cleaning the corroded aluminum foil with deionized water, removing the nitrous acid remained on the surface, and drying at 100 ℃ for 5 hours. And (3) flatly laying the dried aluminum foil, putting the aluminum foil into a heating area of a PECVD tubular atmosphere furnace, and introducing helium gas to thoroughly clean and remove air in the furnace chamber. And vacuumizing the furnace chamber, and then introducing ethane and helium, wherein the flow rate of ethane is 50sccm, the flow rate of helium is 50sccm, and the furnace chamber generates certain air pressure which is controlled within the range of 2 Pa-100 Pa. And starting microwave plasma with the power of 1000W, heating to 700 ℃ at the speed of 50 ℃/min, preserving heat for 3 hours, depositing carbon source molecules on the surface of the aluminum foil through pyrolysis, growing to form graphene, and cooling to obtain the graphene-modified aluminum foil.
Example 3
The embodiment provides a preparation method of a graphene layer modified aluminum foil with high peel strength, which comprises the following steps:
1. and (3) putting an aluminum foil with the thickness of 30 mu m into oxalic acid, soaking for 2min at the temperature of 60 ℃ to enable part of an aluminum oxide layer on the surface of the aluminum foil to perform corrosion reaction with the oxalic acid to form a rough surface structure.
2. Repeatedly cleaning the corroded aluminum foil with deionized water, removing oxalic acid remained on the surface, and drying at 80 ℃ for 3 hours. And (3) flatly laying the dried aluminum foil, putting the aluminum foil into a heating area of a PECVD tubular atmosphere furnace, and introducing nitrogen to thoroughly clean and remove air in the furnace chamber. And vacuumizing the furnace chamber, and then introducing acetylene and nitrogen, wherein the flow rate of the acetylene is 25sccm, the flow rate of the nitrogen is 50sccm, and the furnace chamber generates certain air pressure, and the air pressure is controlled within the range of 2 Pa-100 Pa. And (3) starting direct-current high-voltage plasma with the power of 500W, heating to 600 ℃ at the speed of 25 ℃/min, preserving heat for 2 hours, depositing carbon source molecules on the surface of the aluminum foil through pyrolysis, growing to form graphene, and cooling to obtain the graphene-modified aluminum foil.
Comparative example 1
The embodiment provides a preparation method of a conventional graphene layer modified aluminum foil, which comprises the following steps:
basically according to the chemicals and parameters of example 1, except that the aluminum foil was not corroded, graphene growth was performed directly in a PECVD tube atmosphere furnace.
The peel strength values of the samples before and after improvement are shown in the following table.
Table 1 peel strength values for samples before and after improvement
| Peel strength (N/m) | |
| Example 1 | 22.1 |
| Example 2 | 21.2 |
| Example 3 | 23.5 |
| Comparative example 1 | 4.9 |
From the table, the peel strength of the sample after improvement is obviously higher than that before improvement, which indicates that the peel strength of the graphene layer and the aluminum foil through the method of the invention is obviously improved.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and those skilled in the art may modify or substitute the technical solution of the present invention without departing from the spirit and scope of the present invention, and the protection scope of the present invention shall be defined by the claims.
Claims (10)
1. The preparation method of the graphene layer modified aluminum foil is characterized by comprising the following steps of:
s1, placing an aluminum foil into a treatment liquid, enabling an aluminum oxide layer on the surface of the aluminum foil to perform corrosion reaction with the treatment liquid, controlling the reaction time, and enabling the aluminum oxide on the surface layer to react and dissolve to form a rough surface structure;
s2, cleaning the corroded aluminum foil with deionized water, drying, spreading and placing in a heating area of a PECVD (plasma chemical vapor deposition) tubular atmosphere furnace, and introducing non-oxidizing gas to thoroughly clean and remove air in a furnace chamber;
s3, vacuumizing the furnace chamber, and then introducing a carbon source and non-oxidizing gas to enable the furnace chamber to generate certain air pressure, wherein the non-oxidizing gas is carrier gas of the carbon source, and conveying the carbon source to a heating area of the PECVD tubular atmosphere furnace;
and S4, starting plasma, heating to the growth temperature of plasma chemical vapor deposition, preserving heat for 10 min-3 h, depositing carbon source molecules on the surface of the aluminum foil through pyrolysis, growing to form graphene, and cooling to obtain the graphene-modified aluminum foil.
2. The method according to claim 1, wherein the treatment liquid is one or more of phosphoric acid, nitrous acid and oxalic acid.
3. The preparation method according to claim 1 or 2, wherein in the step S1, the reaction time is controlled to be 20S-3min and the reaction temperature is controlled to be 40-70 ℃.
4. A method according to any one of claims 1 to 3, wherein the graphene layer modified aluminum foil contains C-O-Al covalent bonds.
5. The method according to any one of claims 1 to 4, wherein the aluminum foil has a thickness of 10 to 50 μm.
6. The method according to any one of claims 1 to 5, wherein in the step S2, the drying temperature is 50 to 100 ℃ and the drying time is 10min to 5h;
in the step S2, the non-oxidizing gas is one or more of argon, helium or nitrogen.
7. The production method according to any one of claims 1 to 6, wherein the carbon source gas is selected from one or more of methane, ethane and acetylene.
8. The production method according to any one of claims 1 to 7, wherein the flow rate of the carbon source gas is 0.02sccm to 50sccm;
the percentage content of the carbon source in the total volume of the carbon source and the non-oxidizing gas may be 0.1% to 100%.
9. The method according to any one of claims 1 to 8, wherein in the step S3, the gas pressure after the introduction of the carbon source and the non-oxidizing gas is 2Pa to 100Pa.
10. The method according to any one of claims 1 to 9, wherein in the step S4, the growth temperature of the plasma chemical vapor deposition is 400 ℃ to 700 ℃, and the temperature rising rate is 1 ℃/min to 50 ℃/min.
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