CN101220485A - 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
- Publication number
- CN101220485A CN101220485A CNA2007100359160A CN200710035916A CN101220485A CN 101220485 A CN101220485 A CN 101220485A CN A2007100359160 A CNA2007100359160 A CN A2007100359160A CN 200710035916 A CN200710035916 A CN 200710035916A CN 101220485 A CN101220485 A CN 101220485A
- Authority
- CN
- China
- Prior art keywords
- carbon
- carbon anode
- vapor deposition
- chemical vapor
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Battery Electrode And Active Subsutance (AREA)
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 the penetration 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:
Embodiment 1
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 10Pa 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 obtains and tight, the uniform pyrocarbon coating of thickness of matrix bond; 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 ℃,＜the 10Pa vacuum under thermal treatment 8～16h, obtain the pyrolytic carbon polarization resistant coating that pyrocarbon coating and metal particle mix and combine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710035916A CN100590229C (en) | 2007-10-17 | 2007-10-17 | Method for manufacturing fluorine carbon anode chemical vapor deposition pyrolytic carbon polarization resistant coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710035916A CN100590229C (en) | 2007-10-17 | 2007-10-17 | Method for manufacturing fluorine carbon anode chemical vapor deposition pyrolytic carbon polarization resistant coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101220485A true CN101220485A (en) | 2008-07-16 |
| CN100590229C CN100590229C (en) | 2010-02-17 |
Family
ID=39630549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710035916A Expired - Fee Related CN100590229C (en) | 2007-10-17 | 2007-10-17 | Method for manufacturing fluorine carbon anode chemical vapor deposition pyrolytic carbon polarization resistant coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100590229C (en) |
Cited By (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 |
| CN111172555A (en) * | 2020-01-22 | 2020-05-19 | 核工业第八研究所 | Carbon anode plate for fluorine production |
| CN112513333A (en) * | 2018-08-03 | 2021-03-16 | 昭和电工株式会社 | Anode for electrolytic synthesis, and method for producing fluorine gas or fluorine-containing compound |
| CN113366154A (en) * | 2019-02-06 | 2021-09-07 | 尤里·瓦西列维奇·塔拉索夫 | Non-consumable anode for electrolysis |
-
2007
- 2007-10-17 CN CN200710035916A patent/CN100590229C/en not_active Expired - Fee Related
Cited By (5)
| 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 |
| CN112513333A (en) * | 2018-08-03 | 2021-03-16 | 昭和电工株式会社 | Anode for electrolytic synthesis, and method for producing fluorine gas or fluorine-containing compound |
| CN113366154A (en) * | 2019-02-06 | 2021-09-07 | 尤里·瓦西列维奇·塔拉索夫 | Non-consumable anode for electrolysis |
| CN111172555A (en) * | 2020-01-22 | 2020-05-19 | 核工业第八研究所 | Carbon anode plate for fluorine production |
| CN111172555B (en) * | 2020-01-22 | 2022-11-08 | 核工业第八研究所 | Carbon anode plate for fluorine production |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100590229C (en) | 2010-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | Tuning the electrochemical reactivity of boron‐and nitrogen‐substituted graphene | |
| Song et al. | Halogen‐doped carbon dots on amorphous cobalt phosphide as robust electrocatalysts for overall water splitting | |
| Cui et al. | Single layer graphene encapsulating non-precious metals as high-performance electrocatalysts for water oxidation | |
| CN102648308B (en) | Ozone generating apparatus | |
| Tong et al. | Trace level Co–N doped graphite foams as high-performance self-standing electrocatalytic electrodes for hydrogen and oxygen evolution | |
| CA2966834C (en) | Oxygen-generating anode | |
| CN101800318B (en) | Metal bipolar plate for proton exchange membrane fuel cell and preparation method thereof | |
| CN100590229C (en) | Method for manufacturing fluorine carbon anode chemical vapor deposition pyrolytic carbon polarization resistant coating | |
| Bang et al. | Heterostructured Mo2N–Mo2C Nanoparticles Coupled with N‐Doped Carbonized Wood to Accelerate the Hydrogen Evolution Reaction | |
| WO2018120601A1 (en) | Preparation method for self-supporting thin film of graphene-enhanced three-dimensional porous carbon | |
| CN108178151B (en) | Preparation method of graphene composite structure material | |
| CN110803743B (en) | Preparation method of defect-state titanium oxide-aluminum oxide-graphene ceramic electrode | |
| CN104894595A (en) | High-catalytic-activity amorphous metal oxide hydrogen evolution electrode and preparation method thereof | |
| CN111155302B (en) | Graphene composite carbon fiber and PECVD (plasma enhanced chemical vapor deposition) preparation method thereof | |
| CN108314013B (en) | Regular porous graphene thick film and preparation method thereof | |
| CN103906416A (en) | Method for manufacturing artificial graphite radiating film with catalytic graphitization technology | |
| CN101724864B (en) | Preparation method of non-graphitized conductive carbon anode material | |
| CN109868483B (en) | Water electrolytic cell metal bipolar plate with corrosion-resistant protective layer, preparation and application | |
| CN100492736C (en) | Process of producing double pole plates for fuel cell | |
| CN117431082B (en) | Catalytic carbonization method of tar generated by biomass pyrolysis, carbon material and application | |
| Cheng et al. | Concurrent H2 generation and formate production assisted by CO2 absorption in one electrolyzer | |
| CN108914060B (en) | Preparation method of surface protective coating of bipolar plate of fuel cell | |
| Zhang et al. | Core–shell structures of Cu 2 O constructed by carbon quantum dots as high-performance zinc-ion battery cathodes | |
| CN103482625A (en) | Niobium carbide and tantalum carbide electrode preparation method | |
| Christensen et al. | CsH2PO4 as electrolyte for the formation of CH4 by electrochemical reduction of CO2 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100217 Termination date: 20131017 |