GB2271359A - Graphite electrode for use in an electrolytic fluorine cell - Google Patents
Graphite electrode for use in an electrolytic fluorine cell Download PDFInfo
- Publication number
- GB2271359A GB2271359A GB9320467A GB9320467A GB2271359A GB 2271359 A GB2271359 A GB 2271359A GB 9320467 A GB9320467 A GB 9320467A GB 9320467 A GB9320467 A GB 9320467A GB 2271359 A GB2271359 A GB 2271359A
- Authority
- GB
- United Kingdom
- Prior art keywords
- electrode
- carbon
- substrate
- cell
- layer
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 16
- 239000010439 graphite Substances 0.000 title claims abstract description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 21
- 229910052731 fluorine Inorganic materials 0.000 title claims description 21
- 239000011737 fluorine Substances 0.000 title claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 8
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 7
- 239000004005 microsphere Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- 229910000792 Monel Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- POHFBTRVASILTB-UHFFFAOYSA-M potassium;fluoride;dihydrofluoride Chemical compound F.F.[F-].[K+] POHFBTRVASILTB-UHFFFAOYSA-M 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/245—Fluorine; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/043—Carbon, e.g. diamond or graphene
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The electrode comprises a substrate 12 comprising carbon, and a layer on the substrate comprising a multiplicity of graphite particles 18 bonded in a non-graphitic carbon layer 16 to the substrate. The carbon layer 16 comprises vitreous carbon. <IMAGE>
Description
An electrode
This invention relates to an electrode, and more particularly to an electrode for use in the generation of fluorine.
Carbon is one of the few materials suitable for use as an anode in electrolytic fluorine cells. However, carbon eventually becomes non-wetted by the electrolyte due to the build up of a carbon fluoride (CFx)n film and can become polarised. When this occurs the electric current flow through the electrolytic cell drops markedly for a given applied voltage at which electrolysis might previously have been proceeding satisfactorily. Graphite does not suffer from such polarisation effects, but is prone to disintegration in an electrolytic fluorine cell because of its layered crystal structure.
It is an object of the invention to provide an electrode for a fluorine electrolysis cell which utilises graphite as an electrical conductor but with an improved structural stability.
According to the present invention there is provided an electrode for use in an electrolytic fluorine cell, the electrode comprising a substrate comprising carbon, and a layer on the substrate comprising a multiplicity of graphite particles bonded in a non-graphitic carbon layer to the substrate. Preferably, the carbon layer comprises vitreous carbon.
Preferably, the graphite particles comprise microspheres thereof, desirably of size 10 microns or less.
The invention also includes an electrylytic cell for the production of fluorine having an electrode according to the invention, and a process for producing fluorine using the electrode of the invention as an anode in an electrolytic fluorine cell.
The invention further includes a method of making an electrode for an electrolytic fluorine cell, the method comprising forming a substrate comprising carbon, and applying to the substrate a layer comprising carbon having a multiplicity of graphite particles bonded thereto.
The invention will not be further described by way of example only with reference to the accompanying drawings, in which:
Figure 1 shows a median side sectional view of an electrode for an electrolytic fluorine cell;
Figure 2 shows to an enlarged scale that part within the circle 'X' of Figure 1, and
Figure 3 shows a diagrammatic representation in medial side section of an electrolytic fluorine cell.
Referring now to Figures 1 and 2, an electrode 10 is shown and comprises a carbon substrate 12 having thereon a layer 14 comprising vitreous carbon 16 to which a multiplicity of graphite microspheres 18 are bonded. A nickel support place 20 is welded to a threaded steel or nickel rod 22 which engages a correspondingly threaded hole 24 in the substrate 12. The nickel support place 20 extends at 26 on to the layer 14 but short of the intended immersion level of the electrode 10. In other respects the electrode 10 is similar to known electrodes used in conventional electrolytic fluorine cells.
Referring to Figure 3, an electrolytic fluorine cell 30 is shown and comprises a steel body 32 which acts as a cathode and is closed by a steel lid 34 from which it is electrically insulated by chloroprene rubber or fluorinated elastomer 36. A nickel or Monel gas separation skirt 38 extends from the lid 34 below the level of an electrolyte 40 (KF.2HF). The skirt 38 prevents mixing of gases produced at the steel body 32 cathode and an anode provided by the electrode 10 of Figures 1 and 2. The interior of the skirt 38 is purged with nitrogen as shown by the arrows. Further details of the cell 30 are conventional and known in the art.
In use of the cell 30, the vitreous carbon 16 in the layer 14 eventually becomes polarised as explained above, but the graphite microspheres 18 provide highly active sites for electrolysis to occur. A graphite intercalation compound (Cx + HF2-) forms on the graphite microspheres 18, but this does not have the same inhibiting effect on current flow that the above-mentioned carbon fluoride film (CFx)n has on he vitreous carbon 16 exposed to the electrolyte 40. As individual graphite microspheres 18 disintegrate, some of their residues are retained by the effectiveness of the bond to the vitreous carbon 16 and, therefore, still provide highly active sites for electrolysis. Eventually when microspheres 18 are completely removed from the layer 14, other microspheres 18 become exposed to the electrolyte 40 so that electrolysis continues.
Because of the greater electrical conductivity of the electrode 10 compared with conventional carbon electrodes used in electrolytic fluorine cells, such cells 30 using the electrode 10 should be able to operate at a higher current density at the same voltage as hitherto, or at a lower voltage at the same current density as hitherto. Use of the electrode 10 should raise the limit at which the onset of anode polarisation effects occur.
It will be understood that features of the electrode 10 may be changed, for example, to suit individual electrolytic fluorine cells provided that the feature of the invention (ie the substrate 12 and the layer 14) are retained. For example, the layer 14 need not extend to the nickel extension 26 provided that the layer 14 extends above the intended depth of immersion of the electrode 10 in the electrolyte 40. It will be appreciated that completely spherical microspheres 18 are not essential, and graphite particles having other shapes may be satisfactory.
An example of an electrolytic fluorine cell is described in British Patent Specification No 2135334A.
Claims (7)
1. An electrode for use in an electrolytic fluorine cell, the electrode comprising a substrate comprising carbon, and a layer on the substrate comprising a multiplicity of graphite particles bonded in a non-graphitic carbon layer to the substrate.
2. An electrode as in claim 1 and wherein the carbon layer comprises vitreous carbon.
3. An electrode as in claim 1 or claim 2 and wherein the graphite particles comprise microspheres thereof of size 10 microns or less average diameter.
4. An electrode as in claim 1, 2 or 3 which has been made by forming a substrate comprising carbon, and applying to the substrate a layer comprising carbon having a multiplicity of graphite particles bonded thereto.
5. An electrolytic cell for the production of fluorine having an electrode as in claim 1, 2 or 3.
6. A process for producing fluorine having an electrolytic fluorine cell the said electrode being the anode of the cell.
7. An electrode substantially as hereinbefore described with reference to the accompanying drawings.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB929221102A GB9221102D0 (en) | 1992-10-07 | 1992-10-07 | An electrode |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9320467D0 GB9320467D0 (en) | 1993-11-24 |
| GB2271359A true GB2271359A (en) | 1994-04-13 |
| GB2271359B GB2271359B (en) | 1995-10-18 |
Family
ID=10723110
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB929221102A Pending GB9221102D0 (en) | 1992-10-07 | 1992-10-07 | An electrode |
| GB9320467A Expired - Fee Related GB2271359B (en) | 1992-10-07 | 1993-10-05 | An electrode |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB929221102A Pending GB9221102D0 (en) | 1992-10-07 | 1992-10-07 | An electrode |
Country Status (1)
| Country | Link |
|---|---|
| GB (2) | GB9221102D0 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2213770A1 (en) * | 2009-02-02 | 2010-08-04 | Permelec Electrode Ltd. | Anode for electrolysis and method of electrolytically synthesizing fluorine-containing substance using the anode for electrolysis |
| CN105755499A (en) * | 2016-03-31 | 2016-07-13 | 张玲 | Method for electrolytic preparation of sulfur hexafluoride |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB674731A (en) * | 1949-04-29 | 1952-07-02 | C D Patents Ltd | Improved electro-chemical electrode |
| GB2135334A (en) * | 1983-02-24 | 1984-08-30 | British Nuclear Fuels Plc | Composite carbon electrode |
| EP0219877A1 (en) * | 1985-10-24 | 1987-04-29 | Norsk Hydro A/S | Laminated carbon cathode for cells for the production of aluminium by electrolytic smelting |
| US4816338A (en) * | 1986-06-10 | 1989-03-28 | Denki Kagaku Kogyo Kabushiki Kaisha | Glassy carbon-coated article |
| EP0311538A1 (en) * | 1987-10-06 | 1989-04-12 | SERS SOCIETE DES ELECTRODES & REFRACTAIRES SAVOIE | Process and apparatus for the continuous and simultaneous graphitisation of long carbonaceous bodies and of carbonaceous grains moving counter-currently |
-
1992
- 1992-10-07 GB GB929221102A patent/GB9221102D0/en active Pending
-
1993
- 1993-10-05 GB GB9320467A patent/GB2271359B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB674731A (en) * | 1949-04-29 | 1952-07-02 | C D Patents Ltd | Improved electro-chemical electrode |
| GB2135334A (en) * | 1983-02-24 | 1984-08-30 | British Nuclear Fuels Plc | Composite carbon electrode |
| EP0219877A1 (en) * | 1985-10-24 | 1987-04-29 | Norsk Hydro A/S | Laminated carbon cathode for cells for the production of aluminium by electrolytic smelting |
| US4816338A (en) * | 1986-06-10 | 1989-03-28 | Denki Kagaku Kogyo Kabushiki Kaisha | Glassy carbon-coated article |
| EP0311538A1 (en) * | 1987-10-06 | 1989-04-12 | SERS SOCIETE DES ELECTRODES & REFRACTAIRES SAVOIE | Process and apparatus for the continuous and simultaneous graphitisation of long carbonaceous bodies and of carbonaceous grains moving counter-currently |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2213770A1 (en) * | 2009-02-02 | 2010-08-04 | Permelec Electrode Ltd. | Anode for electrolysis and method of electrolytically synthesizing fluorine-containing substance using the anode for electrolysis |
| CN105755499A (en) * | 2016-03-31 | 2016-07-13 | 张玲 | Method for electrolytic preparation of sulfur hexafluoride |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9320467D0 (en) | 1993-11-24 |
| GB9221102D0 (en) | 1992-11-18 |
| GB2271359B (en) | 1995-10-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20011005 |