CN100590229C - Method for manufacturing fluorine carbon anode chemical vapor deposition pyrolytic carbon polarization resistant coating - Google Patents
Method for manufacturing fluorine carbon anode chemical vapor deposition pyrolytic carbon polarization resistant coating Download PDFInfo
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- CN100590229C CN100590229C CN200710035916A CN200710035916A CN100590229C CN 100590229 C CN100590229 C CN 100590229C CN 200710035916 A CN200710035916 A CN 200710035916A CN 200710035916 A CN200710035916 A CN 200710035916A CN 100590229 C CN100590229 C CN 100590229C
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Abstract
A preparing method of fluorine manufacturing carbon anode chemical vapor deposition pyrolytic carbon anti-polarization coating adopts C3H6 and N2 as carbon sources to do chemical vapor deposition to the carbon anode, thus getting the pyrolytic carbon coating. The method adopts nickel nitrate as electroplating solution to electroplate the carbon anode with the pyrolytic carbon coating, and after the electroplating, the carbon anode is cleaned and dried by ultrasound. After heat treatment under vacuum, the pyrolytic carbon anti-polarization coating which is combined by pyrolytic carbon coating and metal particle adulteration can be obtained. Adopting the invention, the obtained chemical vapor deposition pyrolytic carbon coating has the advantages of uniform thickness and close combination with the carbon anode matrix; the surface holes of the carbon anode are sealed by chemical vapor deposition pyrolytic carbon which is of low graphitization and difficult polarization, thus avoiding thepenetration of the electrolyte to the inside of the electrode and protecting the inner structure of the electrode; surface metal particle adulteration layer is formed, thus preventing the production of non-conductive graphite fluoride and promoting the conductivity of the surface; the current density in the anode is 0.1mA/cm<2>, thus effectively preventing the polarization of the carbon anode.
Description
Technical field
The present invention relates to the anti-Polarization technique in a kind of system fluorine carbon anode surface, particularly a kind of system fluorine carbon anode chemical vapor deposition pyrolytic carbon polarization resistant coating production.
Background technology
The system fluorine carbon anode is a kind of advanced carbon material that is made of decolorizing carbon, has high strength, low degree of graphitization, low resistivity, anticorrosive, and characteristics such as especially anti-fluorine gas corrosion are the critical materials of industrial electrolysis system fluorine.Fluorine gas is mainly used in nuclear industry, is the main industrial chemicals of producing nuclear fuel.Along with nuclear industry development to the increasing rapidly of fluorine gas demand, require the system fluorine carbon anode to possess higher system fluorine efficient (anodic current density and steadily the cycle of operation).
The principal element that restriction carbon anode system fluorine efficient improves is the polarization of carbon anode.So-called polarization is meant: during electrolysis system fluorine, fluorine gas that produces in the electrolyzer and the reaction of the greying constituent element in the carbon anode are at the rete of anode surface generation based on covalent type fluorographite (CFX).This fluorographite hinders electron migration, significantly reduces the wettability of KF-2HF electrolytic solution antianode, is the compound of a kind of insulation or poor electric conductivity.Its existence will sharply reduce electrolytic efficiency, make system fluorine process hard to carry on.Meanwhile, follow the swelling that polarizes and come, will cause the local disengaging of carbon anode plate, fracture.
The anti-Polarization technique of system fluorine carbon anode of current main employing is the non-graphitized technology of carbon anode matrix.Promptly pass through the non-graphitized of each constituent element of carbon anode, delay polarization process, improve the carbon anode life-span.But because carbon is a kind of heterogeneous body mixture, can unavoidably sneak into the greying constituent element in the Industrial processes, the effect of this method is often not good enough; And because the conductivity of carbon material reduces with degree of graphitization, the non-graphitized conductivity that also will reduce carbon anode of matrix influences anodic current density and improves.
Summary of the invention
In order to solve the polarization problem of system fluorine carbon anode, the invention provides the difficult polarization of a kind of system fluorine carbon anode chemical vapor deposition pyrocarbon coating preparation method, improve the anti-polarization performance of carbon anode.
System fluorine carbon anode chemical vapor deposition pyrolytic carbon polarization resistant coating production comprises the steps:
Adopt ultrasonic cleaning carbon anode surface blot; Press gas volume per-cent: C
3H
635%～65%, N
265%～35% preparation carbon source gas; Carbon anode is placed chemical vapor deposition stove, and at 800～1200 ℃ of furnace temperature, furnace pressure 0.5～5KPa deposit 1～20h, the control furnace gas flows to, and obtains and tight, the uniform pyrocarbon coating of thickness of matrix bond; By concentration 1.5mol/l preparation nickel nitrate aqueous solution,, carbon anode is placed above-mentioned electroplate liquid, with current density 0.6mA/cm as electroplate liquid
2Electroplate 5～15min; Ultrasonic cleaning carbon anode surface blot, oven dry; 1040 ℃,＜the 10Pa vacuum under thermal treatment 8～16h, obtain the pyrolytic carbon polarization resistant coating that pyrocarbon coating and metal particle mix and combine.
Adopt the present invention, gained chemical vapor deposition pyrolytic carbon coat-thickness is even, tight with the carbon anode matrix bond; With low greying, difficult polar chemical vapor deposition pyrolytic carbon sealing carbon anode surface pore, stop electrolytic solution to infiltrate the guard electrode internal structure to electrode interior; Form surface metal particle doped layer, formation conductive ion type or half ionic graphite intercalation compound layer when helping electrolysis system fluorine (CX ' F), stop the generation of non-conductive fluorographite, improve the surface conduction performance, anodic current density is greater than 0.1mA/cm
2, effectively prevent the polarization of carbon anode plate; The chemical vapor deposition pyrolytic carbon coating is mixed with the metal particle and is combined, and improves the anti-polarization performance of carbon anode jointly.
Embodiment
Provide following examples in conjunction with content of the present invention:
EXAMPLE l
At first, ultrasonic cleaning carbon anode surface blot, oven dry.Secondly, press gas volume per-cent: C
3H
635%, N
265% preparation carbon source gas.Carbon anode is placed chemical vapor deposition stove, and 800 ℃ of furnace temperature of control, furnace pressure 5Kpa and furnace gas flow to, deposition 20h.Once more, by concentration 1.5mol/l preparation nickel nitrate aqueous solution, carbon anode is placed electroplate liquid, with current density 0.6mA/cm
2Electroplate 5min.Ultrasonic cleaning carbon anode surface blot and oven dry.At last, 1040 ℃,＜the 10Pa vacuum under thermal treatment 8h.
Embodiment 2
At first, ultrasonic cleaning carbon anode surface blot, oven dry.Secondly, press gas volume per-cent: C
3H
635%, N
265% preparation carbon source gas.Carbon anode is placed chemical vapor deposition stove, and 1000 ℃ of furnace temperature of control, furnace pressure 3Kpa and furnace gas flow to, deposition 10h.Once more, by concentration 1.5mol/l preparation nickel nitrate aqueous solution, carbon anode is placed electroplate liquid, with current density 0.6mA/cm
2Electroplate 10min.Ultrasonic cleaning carbon anode surface blot and oven dry.At last, 1040 ℃,＜the 10Pa vacuum under thermal treatment 12h.
Embodiment 3
At first, ultrasonic cleaning carbon anode surface blot, oven dry.Secondly, press gas volume per-cent: C
3H
635%, N
265% preparation carbon source gas.Carbon anode is placed chemical vapor deposition stove, and 1200 ℃ of furnace temperature of control, furnace pressure 1Kpa and furnace gas flow to, deposition 1h.Once more, by concentration 1.5mol/l preparation nickel nitrate aqueous solution, carbon anode is placed electroplate liquid, with current density 0.6mA/cm
2Electroplate 15min.Ultrasonic cleaning carbon anode surface blot and oven dry.At last, 1040 ℃,＜the l0Pa vacuum under thermal treatment 16h.
Embodiment 4
At first, ultrasonic cleaning carbon anode surface blot, oven dry.Secondly, press gas volume per-cent: C
3H
650%, N
250% preparation carbon source gas.Carbon anode is placed chemical vapor deposition stove, and 900 ℃ of furnace temperature of control, furnace pressure 3Kpa and furnace gas flow to, deposition 5h.Once more, by concentration 1.5mol/l preparation nickel nitrate aqueous solution, carbon anode is placed electroplate liquid, with current density 0.6mA/cm
2Electroplate 8min.Ultrasonic cleaning carbon anode surface blot and oven dry.At last, 1040 ℃,＜the 10Pa vacuum under thermal treatment 9h.
Embodiment 5
At first, ultrasonic cleaning carbon anode surface blot, oven dry.Secondly, press gas volume per-cent: C
3H
650%, N
250% preparation carbon source gas.Carbon anode is placed chemical vapor deposition stove, and 1100 ℃ of furnace temperature of control, furnace pressure 2Kpa and furnace gas flow to, deposition 3h.Once more, by concentration 1.5mol/l preparation nickel nitrate aqueous solution, carbon anode is placed electroplate liquid, with current density 0.6mA/cm
2Electroplate 12min.Ultrasonic cleaning carbon anode surface blot and oven dry.At last, 1040 ℃,＜the 10Pa vacuum under thermal treatment 13h.
Embodiment 6
At first, ultrasonic cleaning carbon anode surface blot, oven dry.Secondly, press gas volume per-cent: C
3H
665%, N
235% preparation carbon source gas.Carbon anode is placed chemical vapor deposition stove, and 800 ℃ of furnace temperature of control, furnace pressure 4Kpa and furnace gas flow to, deposition 12h.Once more, by concentration 1.5mol/l preparation nickel nitrate aqueous solution, carbon anode is placed electroplate liquid, with current density 0.6mA/cm
2Electroplate 5min.Ultrasonic cleaning carbon anode surface blot and oven dry.At last, 1040 ℃,＜the 10Pa vacuum under thermal treatment 9h.
Embodiment 7
At first, ultrasonic cleaning carbon anode surface blot, oven dry.Secondly, press gas volume per-cent: C
3H
665%, N
235% preparation carbon source gas.Carbon anode is placed chemical vapor deposition stove, and 900 ℃ of furnace temperature of control, furnace pressure 2Kpa and furnace gas flow to, deposition 8h.Once more, by concentration 1.5mol/l preparation nickel nitrate aqueous solution, carbon anode is placed electroplate liquid, with current density 0.6mA/cm
2Electroplate 10min.Ultrasonic cleaning carbon anode surface blot and oven dry.At last, 1040 ℃,＜the 10Pa vacuum under thermal treatment 12h.
Embodiment 8
At first, ultrasonic cleaning carbon anode surface blot, oven dry.Secondly, press gas volume per-cent: C
3H
665%, N
235% preparation carbon source gas.Carbon anode is placed chemical vapor deposition stove, and 1000 ℃ of furnace temperature of control, furnace pressure 1Kpa and furnace gas flow to, deposition 5h.Once more, by concentration 1.5mol/l preparation nickel nitrate aqueous solution, carbon anode is placed electroplate liquid, with current density 0.6mA/cm
2Electroplate 15min.Ultrasonic cleaning carbon anode surface blot and oven dry.At last, 1040 ℃,＜the 10Pa vacuum under thermal treatment 16h.
Claims (1)
1. system fluorine carbon anode chemical vapor deposition pyrolytic carbon polarization resistant coating production is characterized in that: adopt ultrasonic cleaning carbon anode surface blot; Press gas volume per-cent: C
3H
635%～65%, N
265%～35% preparation carbon source gas; Carbon anode is placed chemical vapor deposition stove, and at 800～1200 ℃ of furnace temperature, furnace pressure 0.5～5KPa deposit 1～20h, the control furnace gas flows to, and acquisition combines closely with carbon anode, the uniform pyrocarbon coating of thickness; By concentration 1.5mol/l preparation nickel nitrate aqueous solution,, will contain the pyrocarbon coating carbon anode and place above-mentioned electroplate liquid, with current density 0.6mA/cm as electroplate liquid
2Electroplate 5～15min; Ultrasonic cleaning carbon anode surface blot, oven dry; 1040 ℃, less than the 10Pa vacuum under thermal treatment 8～16h, obtain the pyrolytic carbon polarization resistant coating that pyrocarbon coating and metal particle mix and combine.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200710035916A CN100590229C (en) | 2007-10-17 | 2007-10-17 | Method for manufacturing fluorine carbon anode chemical vapor deposition pyrolytic carbon polarization resistant coating |
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|---|---|---|---|
| CN200710035916A CN100590229C (en) | 2007-10-17 | 2007-10-17 | Method for manufacturing fluorine carbon anode chemical vapor deposition pyrolytic carbon polarization resistant coating |
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| CN100590229C true CN100590229C (en) | 2010-02-17 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724864B (en) * | 2010-01-14 | 2011-05-18 | 中南大学 | Preparation method of non-graphitized conductive carbon anode material |
| EP3831984A4 (en) * | 2018-08-03 | 2021-09-29 | Showa Denko K.K. | Anode for electrolytic synthesis and method for manufacturing fluorine gas or fluorine-containing compound |
| RU2700921C1 (en) * | 2019-02-06 | 2019-09-24 | Юрий Васильевич Тарасов | Non-consumable anode for electrolysis |
| CN111172555B (en) * | 2020-01-22 | 2022-11-08 | 核工业第八研究所 | Carbon anode plate for fluorine production |
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2007
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Non-Patent Citations (4)
| Title |
|---|
| 工艺条件对C/C复合材料可石墨化性的影响. 谢志勇等.矿冶工程，第25卷第2期. 2005 |
| 工艺条件对C/C复合材料可石墨化性的影响. 谢志勇等.矿冶工程，第25卷第2期. 2005 * |
| 电解制氟中碳电极极化及其应对措施. 冀延治等.舰船科学技术，第28卷第2期. 2006 |
| 电解制氟中碳电极极化及其应对措施. 冀延治等.舰船科学技术，第28卷第2期. 2006 * |
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