CN114231897A - Carbon film current collector produced by vacuum magnetron sputtering and preparation method thereof - Google Patents
Carbon film current collector produced by vacuum magnetron sputtering and preparation method thereof Download PDFInfo
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- CN114231897A CN114231897A CN202111565041.1A CN202111565041A CN114231897A CN 114231897 A CN114231897 A CN 114231897A CN 202111565041 A CN202111565041 A CN 202111565041A CN 114231897 A CN114231897 A CN 114231897A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 79
- 238000001755 magnetron sputter deposition Methods 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000011888 foil Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 20
- 239000010439 graphite Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000010884 ion-beam technique Methods 0.000 claims abstract description 10
- 238000005507 spraying Methods 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- 238000004544 sputter deposition Methods 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 239000011889 copper foil Substances 0.000 claims description 9
- 239000013077 target material Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000006056 electrooxidation reaction Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000011253 protective coating Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0605—Carbon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention is applicable to the technical field of current collector preparation, and discloses a carbon film current collector produced by vacuum magnetron sputtering and a preparation method thereof, wherein the preparation method is carried out in a vacuum chamber and comprises the following steps: 1) carrying out plasma cleaning on impurities, oxide films and surface inclusions on the surface of the current collector metal foil by using ion beams; 2) spraying a high-density carbon layer on the cleaned surface of the step 1) by using first magnetron sputtering in vacuum on a current collector metal foil, and coating a first high-density carbon layer; 3) and (3) taking high-purity graphite as a magnetron target, spraying a dense carbon coating on the high-density carbon layer by using second magnetron sputtering in vacuum, and coating a second graphite carbon film to obtain the carbon film current collector. The carbon film current collector manufactured according to the method can obtain the minimum contact resistance value, and the obtained current collector has higher chemical corrosion resistance.
Description
Technical Field
The invention belongs to the technical field of current collector preparation, and particularly relates to a carbon film current collector produced by vacuum magnetron sputtering and a preparation method thereof.
Background
In an electrochemical power source, a current collector mainly functions to introduce current to an active material during charging and to lead current of the active material to a load during discharging, and is a base metal for attaching the active material to a positive electrode or a negative electrode of a battery, such as copper foil and aluminum foil for the positive electrode and the negative electrode.
The surfaces of aluminum foils and copper foils used in the production of electrochemical power sources are contaminated, oxidized films and external dopants. Taking an aluminum foil as an example, as shown in fig. 1, the aluminum foil has AlFeSi and Al3Fe dopants on the surface. These inclusions embedded in the foil body can damage the oxide layer surface or penetrate the oxide layer. In the presence of these inclusions, the presence of the electrolyte causes electrochemical reactions that destroy the aluminum foil to form alumina or hydroxides. Only pure, inclusion-free aluminum has the best resistance to chemical corrosion.
Contact resistance exists between a metal with good conductivity and an active electrode of an electrochemical storage device such as a battery, a supercapacitor, and a fuel cell, and the contact resistance is increased by the presence of an oxide film on the surface of a metal foil. This results in an increase in internal resistance and local heating of the contact point between the metal foil and the active electrode.
In order to eliminate the above disadvantages of electrochemical storage devices, i.e. the disadvantages of unwanted electrochemical corrosion and high potential contact resistance of contact points, the present invention provides a carbon film current collector produced by vacuum magnetron sputtering and a preparation method thereof.
Disclosure of Invention
The embodiment of the invention provides a carbon film current collector produced by vacuum magnetron sputtering and a preparation method thereof, aiming at overcoming the defects of unnecessary electrochemical corrosion, high-order contact resistance of a contact point and the like, reducing the degradation of a negative electrode material, increasing the energy and power density of an applied chemical battery and prolonging the service life (the number of charge-discharge cycles).
The embodiment of the invention is realized as follows:
a method for preparing a carbon film current collector produced by vacuum magnetron sputtering is carried out in a vacuum chamber and comprises the following steps:
1) carrying out plasma cleaning on impurities, oxide films and surface inclusions on the surface of the current collector metal foil by using ion beams;
2) spraying a high-density carbon layer on the cleaned surface of the step 1) by using first magnetron sputtering in vacuum on a current collector metal foil, and coating a first high-density carbon layer;
3) and (3) taking high-purity graphite as a magnetron target, spraying a dense carbon coating on the high-density carbon layer by using second magnetron sputtering in vacuum, and coating a second graphite carbon film to obtain the carbon film current collector.
As a preferred embodiment, the vacuum conditions in the vacuum chamber are: the background vacuum degree of the vacuum chamber is better than 5.0 multiplied by 10-4Pa, the working gas is argon with the purity of 99.99 percent, and the flow rate of the argon is 15-18 sccm.
The ion beam in the step 1) is generated by using an ion gun or a reverse magnetron.
The cleaning condition in the step 1), preferably, the energy of the ion beam is controlled to be 220eV-230 eV.
In the step 1), the current collector is a copper foil or an aluminum foil, the thickness of the copper foil is preferably 0.008mm, and the thickness of the aluminum foil is preferably 0.012mm-0.015 mm.
The first magnetron sputtering in the step 2) is preferably radio frequency magnetron sputtering.
The radio frequency magnetron sputtering power is 50W-150W, the target material used for sputtering is a carbon target with the purity of 99.99%, and the sputtering pressure is 8Pa-12 Pa.
The thickness of the first high-density carbon layer in the step 2) is 3 nm-15 nm. The high density carbon layer has excellent conductivity and acts as a protective layer to minimize aluminum and copper damage from the electrolyte.
The second magnetron sputtering method in step 3) is preferably direct current magnetron sputtering.
The direct current magnetron sputtering adopts 60-80W of sputtering power, the target material used for sputtering is a graphite target with the purity of 99.99 percent, and the sputtering pressure is 12-15 Pa.
The thickness of the second layer of graphite carbon film in the step 3) is 20 nm-120 nm.
A carbon film current collector is prepared by the preparation method.
In vacuum, impurities of iron and silicon compounds appear on the surface of the clean current collector (aluminum foil or copper foil). According to the technical scheme of the invention, a compact carbon film current collector of a first high-density carbon layer and a second graphite carbon film is obtained by a magnetron sputtering method in vacuum; compared with the traditional known protective coating method using electron beams or arc sputtering and the like, the current collector manufactured according to the proposed vacuum magnetron sputtering method can obtain the minimum contact resistance value, and the obtained current collector has higher chemical corrosion resistance.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the method comprises the steps of firstly spraying a high-density carbon layer on a metal foil of a current collector by radio frequency magnetron sputtering on the surface of the cleaned current collector, and coating a first high-density carbon layer; the high-density carbon layer covers impurities on the surface of the cleaned current collector under the condition that the resistance of the current collector is not increased, and the adhesion viscosity of the graphite carbon film layer on the second layer is increased.
2. The second graphite carbon film layer is coated with the thickness of 3-15 nm by direct current magnetron sputtering; the adhesive also has good adhesion viscosity with the first high-density carbon layer; the contact resistance value of the two layers of coatings is only 0.0015-0.00055 ohm/square centimeter, and the resistance value has obvious advantages compared with the traditional coating mode.
3. The carbon coating current collector has higher chemical corrosion resistance.
Drawings
FIG. 1 is a schematic representation of the prior art distribution of deposits on an aluminum foil of a current collector in a humid environment; wherein: al is an aluminum foil layer, P is a deposit (e.g., AlFeSi, Al3Fe), T is a top layer, and B is a barrier layer.
Fig. 2 is a schematic structural diagram of preparation steps of a method for preparing a carbon film current collector for magnetron sputtering carbon coating production, provided by embodiment 1 of the invention; wherein a is an aluminum foil layer containing deposits; b is no high density carbon layer added on the aluminum foil layer; and c is the addition of a graphite carbon film layer.
Fig. 3 is a graph showing the results of detecting the chemical composition of the aluminum foil surface sites of the current collector after step 1) of cleaning in vacuum in example 1 of the present invention; wherein, three sites of 1, 2 and 3 are selected in the figure to detect the chemical components of each point on the surface of the aluminum foil.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention aims to overcome the defects of unnecessary electrochemical corrosion, high potential contact resistance of a contact point and the like, reduce the degradation of a negative electrode material, increase the energy and power density of an applied chemical battery and prolong the service life (the number of charge-discharge cycles). Provides a silicon-carbon negative electrode material for magnetron sputtering carbon coating production and a preparation method thereof.
Example 1
A method for preparing a carbon film current collector produced by vacuum magnetron sputtering is carried out in a vacuum chamber and comprises the following steps:
1) carrying out plasma cleaning on impurities, oxide films and surface inclusions on the surface of the current collector metal foil by using ion beams; as shown in fig. 2 a;
2) spraying a high-density carbon layer on the cleaned surface of the step 1) by using first magnetron sputtering in vacuum on a current collector metal foil, and coating a first high-density carbon layer; as shown in fig. 2 b;
3) spraying a dense carbon coating on the high-density carbon layer by using high-purity graphite as a magnetron target material through second magnetron sputtering in vacuum, and coating a second graphite carbon film to obtain a carbon film current collector; as shown in fig. 2 c.
The vacuum conditions in the vacuum chamber are: the background vacuum degree of the vacuum chamber is better than 5.0 multiplied by 10-4Pa, the working gas is argon with the purity of 99.99 percent, and the flow rate of the argon is 15-18 sccm.
The ion beam in the step 1) is generated by using an ion gun or a reverse magnetron.
The cleaning condition in the step 1) is that the energy of the ion beam is controlled to be 220eV-230 eV. As shown in fig. 3, impurities of iron and silicon compounds appear on the surface of the clean aluminum foil in vacuum.
In the step 1), the current collector is a copper foil or an aluminum foil, the thickness of the copper foil is preferably 0.008mm, and the thickness of the aluminum foil is preferably 0.012mm-0.015 mm.
The first magnetron sputtering in the step 2) is preferably radio frequency magnetron sputtering.
The radio frequency magnetron sputtering power is 50W-150W, the target material used for sputtering is a carbon target with the purity of 99.99%, and the sputtering pressure is 8Pa-12 Pa.
The thickness of the first pure metal coating layer in the step 2) is 3 nm-15 nm. The high density carbon layer has excellent conductivity and acts as a protective layer to minimize aluminum and copper damage from the electrolyte.
The second magnetron sputtering method in step 3) is preferably direct current magnetron sputtering.
The direct current magnetron sputtering adopts 60-80W of sputtering power, the target material used for sputtering is a graphite target with the purity of 99.99 percent, and the sputtering pressure is 12-15 Pa.
The thickness of the second layer of graphite carbon film in the step 3) is 20 nm-120 nm.
A carbon film current collector is prepared by the preparation method.
The method for measuring the contact resistance of the current collector having a dense carbon coating obtained by the above-mentioned preparation method, i.e., the magnetron sputtering method in vacuum, and the results are shown in table 1. Measurements were made on each sample at different compression forces, 2,4 and 6 kg/cm. The current collector manufactured according to the proposed vacuum magnetron sputtering method can obtain a minimum contact resistance value and has a higher resistance to chemical corrosion than known protective coating methods using electron beam coating or arc sputtering.
Table 1 measurement results of contact resistance of current collectors of example 1 and comparative samples
According to the technical scheme of the invention, a current collector with a compact carbon coating is obtained by a magnetron sputtering method in vacuum; compared with the traditional known protective coating method using electron beams or arc sputtering and the like, the current collector manufactured according to the proposed vacuum magnetron sputtering method can obtain the minimum contact resistance value, and the obtained current collector has higher chemical corrosion resistance.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the method comprises the steps of firstly spraying a high-density carbon layer on a metal foil of a current collector by radio frequency magnetron sputtering on the surface of the cleaned current collector, and coating a first high-density carbon layer; the high-density carbon layer covers impurities on the surface of the cleaned current collector under the condition that the resistance of the current collector is not increased, and the adhesion viscosity of the graphite carbon film layer on the second layer is increased.
2. The second graphite carbon film layer is coated with the thickness of 3-15 nm by direct current magnetron sputtering; the adhesive also has good adhesion viscosity with the first high-density carbon layer; the contact resistance value of the two layers of coatings is only 0.0015-0.00055 ohm/square centimeter, and the resistance value has obvious advantages compared with the traditional coating mode.
3. The carbon coating current collector has higher chemical corrosion resistance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method for preparing a carbon film current collector produced by vacuum magnetron sputtering is characterized by comprising the following steps: is carried out in a vacuum chamber and comprises the following steps:
1) carrying out plasma cleaning on impurities, oxide films and surface inclusions on the surface of the current collector metal foil by using ion beams;
2) spraying a high-density carbon layer on the cleaned surface of the step 1) by using first magnetron sputtering in vacuum on a current collector metal foil, and coating a first high-density carbon layer;
3) and (3) taking high-purity graphite as a magnetron target, spraying a dense carbon coating on the high-density carbon layer by using second magnetron sputtering in vacuum, and coating a second graphite carbon film to obtain the carbon film current collector.
2. The method for preparing a carbon film current collector produced by vacuum magnetron sputtering according to claim 1, wherein the method comprises the following steps: the vacuum conditions in the vacuum chamber are: the background vacuum degree of the vacuum chamber is better than 5.0 multiplied by 10-4Pa, the working gas is argon with the purity of 99.99 percent, and the flow rate of the argon is 15-18 sccm.
3. The method for preparing a carbon film current collector produced by vacuum magnetron sputtering according to claim 1, wherein the method comprises the following steps: the ion beam in the step 1) is generated by using an ion gun or a reverse magnetron.
4. The method for preparing a carbon film current collector produced by vacuum magnetron sputtering according to claim 1, wherein the method comprises the following steps: the cleaning condition in the step 1) is that the energy of the ion beam is controlled to be 220eV-230 eV.
5. The method for preparing a carbon film current collector produced by vacuum magnetron sputtering according to claim 1, wherein the method comprises the following steps: in the step 1), the current collector is a copper foil or an aluminum foil, the thickness of the copper foil is 0.008mm, and the thickness of the aluminum foil is 0.012mm-0.015 mm.
6. The method for preparing a carbon film current collector produced by vacuum magnetron sputtering according to claim 1, wherein the method comprises the following steps: the first magnetron sputtering in the step 2) is radio frequency magnetron sputtering;
the radio frequency magnetron sputtering power is 50W-150W, the target material used for sputtering is a carbon target with the purity of 99.99%, and the sputtering pressure is 8Pa-12 Pa.
7. The method for preparing a carbon film current collector produced by vacuum magnetron sputtering according to claim 6, wherein: the thickness of the first high-density carbon layer in the step 2) is 3 nm-15 nm.
8. The method for preparing a carbon film current collector produced by vacuum magnetron sputtering according to claim 1, wherein the method comprises the following steps: the second magnetron sputtering method in the step 3) is direct current magnetron sputtering;
the direct current magnetron sputtering adopts 60-80W of sputtering power, the target material used for sputtering is a graphite target with the purity of 99.99 percent, and the sputtering pressure is 12-15 Pa.
9. The method for preparing a carbon film current collector produced by vacuum magnetron sputtering according to claim 8, wherein: the thickness of the second layer of graphite carbon film in the step 3) is 20 nm-120 nm.
10. A carbon film current collector produced by the production method as recited in any one of claims 1 to 9.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110797545A (en) * | 2019-10-11 | 2020-02-14 | 浙江锋源氢能科技有限公司 | Metal bipolar plate, preparation method thereof and fuel cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110797545A (en) * | 2019-10-11 | 2020-02-14 | 浙江锋源氢能科技有限公司 | Metal bipolar plate, preparation method thereof and fuel cell |
Non-Patent Citations (1)
| Title |
|---|
| 王振廷等主编: "《石墨深加工技术》", 30 June 2017, 哈尔滨工业大学出版社, pages: 51 * |
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