CN100590229C - Method for preparing fluorocarbon anode chemical vapor deposition pyrolytic carbon anti-polarization coating - Google Patents
Method for preparing fluorocarbon anode chemical vapor deposition pyrolytic carbon anti-polarization 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
制氟碳阳极化学气相沉积热解碳抗极化涂层制备方法，采用C3H6和N2为碳源气对碳阳极进行化学气相沉积，获得热解碳涂层；采用硝酸镍水溶液作电镀液，对含热解碳涂层碳阳极电镀，电镀后超声清洗，烘干；真空下热处理，得到热解碳涂层与金属质点掺杂相结合的热解碳抗极化涂层。采用本发明，所得化学气相沉积热解碳涂层厚度均匀、与碳阳极基体结合紧密；以低石墨化、难极化的化学气相沉积热解碳封闭碳阳极表面孔隙，阻止电解液向电极内部渗入，保护电极内部结构；形成表面金属质点掺杂层，阻止不导电氟化石墨的产生，提高表面导电性能，阳极电流密度为0.1mA/cm2，有效防止碳阳极板的极化。A method for preparing a fluorocarbon anode chemical vapor deposition pyrolytic carbon anti-polarization coating, using C 3 H 6 and N 2 as carbon source gases to carry out chemical vapor deposition on a carbon anode to obtain a pyrolytic carbon coating; using nickel nitrate aqueous solution as the The electroplating solution is used for electroplating the carbon anode containing the pyrolytic carbon coating, ultrasonically cleaning and drying after electroplating, and heat treatment under vacuum to obtain the pyrolytic carbon anti-polarization coating combined with the pyrolytic carbon coating and metal particle doping. By adopting the present invention, the obtained chemical vapor deposition pyrolytic carbon coating has a uniform thickness and is closely combined with the carbon anode substrate; the surface pores of the carbon anode are sealed with low graphitization and difficult to polarize chemical vapor deposition pyrolytic carbon, preventing the electrolyte from flowing into the electrode. Infiltrate to protect the internal structure of the electrode; form a doped layer of metal particles on the surface to prevent the generation of non-conductive fluorinated graphite and improve the surface conductivity. The anode current density is 0.1mA/cm 2 , which can effectively prevent the polarization of the carbon anode plate.
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.
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| CN200710035916A CN100590229C (en) | 2007-10-17 | 2007-10-17 | Method for preparing fluorocarbon anode chemical vapor deposition pyrolytic carbon anti-polarization coating |
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| CN100590229C true CN100590229C (en) | 2010-02-17 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101724864B (en) * | 2010-01-14 | 2011-05-18 | 中南大学 | Preparation method of non-graphitized conductive carbon anode material |
| US20210292923A1 (en) * | 2018-08-03 | 2021-09-23 | Showa Denko K.K. | Anode for electrolytic synthesis and method for producing 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 |
| CN119307953B (en) * | 2024-12-17 | 2025-03-28 | 湖南恒升热工机械设备有限公司 | Carbon anode plate for fluorine production and preparation method and application thereof |
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Non-Patent Citations (4)
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| 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 |
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