CA2187364C - Method for the fabrication of an electrochemical cell - Google Patents
Method for the fabrication of an electrochemical cell Download PDFInfo
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- CA2187364C CA2187364C CA002187364A CA2187364A CA2187364C CA 2187364 C CA2187364 C CA 2187364C CA 002187364 A CA002187364 A CA 002187364A CA 2187364 A CA2187364 A CA 2187364A CA 2187364 C CA2187364 C CA 2187364C
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- cell
- cell structure
- polymeric material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/126—Halogenation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/121—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Hybrid Cells (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Secondary Cells (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
A method for the fabrication of an electrochemical cell which has long term chemical stability to anolyte and catholyle solutions at pH's of less than 2 and above 12, which method comprises the steps of: i) thermally processing a polymeric material which exhibits a glass transition and/or melting thermal transition to form the cell structure or components of the cell structure, and ii) subjecting the surfaces of the cell structure or components of the cell structure which, in use, will be in contact with the anolyte and catholyte solutions, to a post halogenation process, whereby the polymeric material forming the said surfaces undergoes halogen substitution to form a chemically stable halogen modified polymeric material.
Description
WO 95/27751 PCTlGB95100667 METHOD FOR THE FABRICATION OF AN
ELECTROCHEMI AL CE L
The present invention relates to a-method for the fabrication of an electrochemical cell and in particular, to a method for the fabrication of an electrochemical cell which has long term chemical resistance and stability to anolyte and catholyte solutions having pH's of less than 1 and/or above 12 at temperatures from ambient to 60Cand which can be formed from thermally processable materials by conventional techniques.
US-A-4485154 discloses an electrically rechargeable anionically active reduction-oxidation electric energy storage-supply system-using a sulfide/polysulfide reaction in one half of the cell and an iodine/polyiodide, chlorine/chloride or bromine/bromide reaction in the other half of the cell. The specification suggeststhat the cell may be operated with the anolyte and catholyte being maintained at slightly basic but near neutral pH's.
We have found that when operating the system with a bromine/bromide couple, very lot: pH's are encountered on the bromine side of the cell and very high pH's on the sulfur side of the cell.
Polytetrafluoroethylene (PTFE) is highly resistant to the action of chemicals-including strong acids and strong alkalis. However, it is not a thermally processable material.
Polyvinylidene fluoride_(PVDF) is a thermoplastic fluorocarbon polymer iahi'ch can be processed by conventional techniques such as compression moulding, injection moulding, extrusion, vacuum forming, rolling and welding. Whilst PVDF is fair y resistant to strong acids it is not stable in strong alkalis.
We have now developed a method for the R'O 95/27751 ~ ~ ~ PCT/GB95/00667 fabrication of an electrochemical cell having chemical resistance and long term stability at both high and low pH's from a thermally processable polymeric material. , Accordingly, the present invention provides a method for the fabrication of an electrochemical cell which has long term chemical stability to anolyte and catholyte solutions at pH's of less than 2, preferably less than 1, and above 12, which method comprises-the steps of:
i) thermally processing a polymeric material-which exhibits a glass transition and/or melting thermal transition to form the cell structure or components of the cell structure, and ii) subjecting the surfaces of the cell.a structure or components of the cell structure which, in use, will be in contact with the anolyte and catholyte solutions, to a post halogenation process,-whereby the polymeric material forming the said surfaces undergoes haloqen substitution to form a chemically stable halogen modified polymeric material.
The polymeric material which is used in step (i) of the present invention may be any material which (a) is thermally.processable and exhibits a glass transition and/or melting thermal transition. The polymeric material preferably has a Newtonian melt viscosity at 150°C and 400 Pascals-of less than 1000 -Pascal seconds, more preferably less than 600 Pascal '. seconds, and (b) when halogenated forms a chemically stable modified polymeric material at its. surface.
Examples. of suitable polymers are high or low density polyethylene, polypropylene or ethylene-propylene copolymers.
The polymeric material may be made into the desired cell structure or components of the cell structure by any of-the pelt knov~:n-techniques,--such as WO 95127751 21 B 7 3 6 ~ P~1GB95/00667 machining of preformed sheets or plates, injection moulding, transfer moulding or compression moulding.
The halogenat-ion process is preferably a fluorination process, although bromination or chlorination processes may also be used. The fluorination is preferably effected by exposing the surfaces which, in use, will be in contactwith the anolyte and catholyte solutions to fluorine gas. The treatment with fluorine gas will preferably be carried out by contacting the surfaces with fluorine gas at a temperature of below 50C. A fluorination process for the production of fluorinated polyethylene film and fluorinated polyethylene containers is disclosed in US-A-2811468 and a similar process may be used in the present invention.
The fluorination may be carried out using an atmosphere containing 1000 fluorine, or the fluorine may be diluted with an inert gas such as nitrogen.
When the halogenation process is a bromination process, this may be effected by exposing the surfaces -to a solution containing bromine. For example, if the cell is to be used as an electrochemical cell in-which one half of the cell uses a bromineJbromidereaction, the surfaces of the cell may effectively be treated by exposing them to the bromine containing solution before the cell is brought into operation..
It will be understoodthat those parts only of the cell structure which, in use, will be in contact with the- anolyte or catholyte need to be subjected to the halogenation process: --Thus; if a complicated cell w, structure is-being fabricated it is possible to post halogenate the cell structure in sections, ensuring that any areas of the structures which are required to be joined together or to any other elements of the cell to form the final cell structure are-not subjected to the halogenatuon process. For example, 2 ~ ~ ~ 3 6 4 PCTlGB9510U667 _ q _ certain areas of the cell structure such as the edges thereof may be masked during the halogenation process.
Alternatively, certain areas-of the cell structure such as the edges thereof may have upstands or sacrificial-beads formed thereon which can be machined off to leave exposed non-halogenated surfaces which can be readily joined to other non-halogenated surfaces by welding or the like. Components of the cell structure may thus be joined in this manner to other elements of the cell such as the cell electrodes or cellmembrane(s).
Alternatively or in addition any elements of the cell structure which would be sensitive to halogenation may be masked prior to the halogenation and the masking removed after the halogenation. For example, the electrodes may be incorporated into appropriate sections of the cell structure prior to the halogenation and masked during the halogenation process-.- The electrodes will then not be affected by the halogenation process and the sections-of the cell structure can then be joined together, or to other elements of the cell, once the masking is renoved.
The present invention also includes within its scope an electrochemical cellwhich has been prepared according to the method of the invention in which the surfaces of the cell structure which, in use,-will be in contact with the anolyte and catholyte solutions have been subjected to a post halogenation treatment to form a chemically stable halogen modified polymeric material.
The present invention will, be-further described with reference to the following Examples:
EXAMPLE 1.
One millimetre thick pieces of high density polyethylene, fluorinated high density polyethylene, WO 95!27751 218 7 3 6 4 PCTIGB95/OU667 high density polyethylene filled with titanium dioxide ' and fluorinated high density polyethylene filled with titanium dioxide were-immersed in a solution of 1.5M
' Brz/3M NaBr and the percentage changes in mass and dimensions with time were measured.
The results are given in Figures 1 to 4. Figures 1 and 2 illustrate the percentage changes in dimension and mass, respectively, for an unfluorinated high density polyethylene. It will be noted from these Figures that initially the polyethylene changed significantly in dimensions and mass as the surface of the polyethylene was brominated by the bromine containing solution. Thereafter the high density polyethylene became relatively stabilized in the solution. Figures 3 and 4 illustrate the percentage changes in-dimension and mass, respectively, for both the filled fluorinated and unfilled fluorinated high density polyethylene samples.-- Figure 4, in particular, illustrates that both the filled fluorinated and unfilled fluorinated high density polyethylene samples are stable in the Brz/NaBr solution after an initial change in mass on immersion in the solution.
~XAMPL~ 2 The permeability to bromine of high density polyethylene (HDPE) with and without a surface fluorine treatment was studied using a method which is a variation of the ASTM test method D26$4.
Polyethylene containers of 25D ml capacity were each partially filled with 200 ml of an aqueous solution of 1.5M bromine in 4M sodium bromide and the containers sealed with fluoroelastomer stoppers. The containers were then each immersed in a glass jar containing 100 ml of a 0.1M aqueous solution of sodium W095127751 ~ ~ ~ PCTlGB95/00667 _ g _ hydroxide.which was also sealed. Throughout each test the vessels were-maintained at either 21°C or 58°C by-immersion in a thermostatically controlled water bath.
At intervals the sodium hydroxide solutions were replaced and the amount of br-omine which had escaped from within each container and which had been trapped by the sodium. hydroxide solutions was determined using ion chromatography. ' This method allowed a direct comparison to be.
l0 made of bromine escape from containers which were identical, except for the surface-fluorination-treatment.
The results are shown in Figure 5 from which it can be seen that the escape of bromine from the untreated HDPE containers began almost immediately and proceeded fairly rapidly,-whilst for zhe fluorinated FL-HDPE containers the escape-ofbromine was significantly delayed and then proceeded only very slowly.
A cell according to the present invention was constructed according to the following method.
Plates of-high density polyethylene were machined in order to provide in the surface or surfaces of each plate the desired profiles to-give-desired cell design. Thus, the plates were machined to provide flow. distributors forthe-electrolytes, flow distribution channels and appropriate holes for the, electrodes:. The electrodes s~Jere then welded into holes provided.in the machined plates, masked and the plates subjected to a--fluorination treatment using fluorine gas mixed with nitrogen in accordance-with the teaching of US Patent No. 2811468.
The masking was then removed from the electrodes.
R'O 95127751 218 l 3 b 4 PCT1GB951Q0667 The fluorinated plates were then separated one from ~ another with cation exchange membranes and a plurality of the plates separated by the membranes were bolted together to form a multi-compartment cell.
. f .
ELECTROCHEMI AL CE L
The present invention relates to a-method for the fabrication of an electrochemical cell and in particular, to a method for the fabrication of an electrochemical cell which has long term chemical resistance and stability to anolyte and catholyte solutions having pH's of less than 1 and/or above 12 at temperatures from ambient to 60Cand which can be formed from thermally processable materials by conventional techniques.
US-A-4485154 discloses an electrically rechargeable anionically active reduction-oxidation electric energy storage-supply system-using a sulfide/polysulfide reaction in one half of the cell and an iodine/polyiodide, chlorine/chloride or bromine/bromide reaction in the other half of the cell. The specification suggeststhat the cell may be operated with the anolyte and catholyte being maintained at slightly basic but near neutral pH's.
We have found that when operating the system with a bromine/bromide couple, very lot: pH's are encountered on the bromine side of the cell and very high pH's on the sulfur side of the cell.
Polytetrafluoroethylene (PTFE) is highly resistant to the action of chemicals-including strong acids and strong alkalis. However, it is not a thermally processable material.
Polyvinylidene fluoride_(PVDF) is a thermoplastic fluorocarbon polymer iahi'ch can be processed by conventional techniques such as compression moulding, injection moulding, extrusion, vacuum forming, rolling and welding. Whilst PVDF is fair y resistant to strong acids it is not stable in strong alkalis.
We have now developed a method for the R'O 95/27751 ~ ~ ~ PCT/GB95/00667 fabrication of an electrochemical cell having chemical resistance and long term stability at both high and low pH's from a thermally processable polymeric material. , Accordingly, the present invention provides a method for the fabrication of an electrochemical cell which has long term chemical stability to anolyte and catholyte solutions at pH's of less than 2, preferably less than 1, and above 12, which method comprises-the steps of:
i) thermally processing a polymeric material-which exhibits a glass transition and/or melting thermal transition to form the cell structure or components of the cell structure, and ii) subjecting the surfaces of the cell.a structure or components of the cell structure which, in use, will be in contact with the anolyte and catholyte solutions, to a post halogenation process,-whereby the polymeric material forming the said surfaces undergoes haloqen substitution to form a chemically stable halogen modified polymeric material.
The polymeric material which is used in step (i) of the present invention may be any material which (a) is thermally.processable and exhibits a glass transition and/or melting thermal transition. The polymeric material preferably has a Newtonian melt viscosity at 150°C and 400 Pascals-of less than 1000 -Pascal seconds, more preferably less than 600 Pascal '. seconds, and (b) when halogenated forms a chemically stable modified polymeric material at its. surface.
Examples. of suitable polymers are high or low density polyethylene, polypropylene or ethylene-propylene copolymers.
The polymeric material may be made into the desired cell structure or components of the cell structure by any of-the pelt knov~:n-techniques,--such as WO 95127751 21 B 7 3 6 ~ P~1GB95/00667 machining of preformed sheets or plates, injection moulding, transfer moulding or compression moulding.
The halogenat-ion process is preferably a fluorination process, although bromination or chlorination processes may also be used. The fluorination is preferably effected by exposing the surfaces which, in use, will be in contactwith the anolyte and catholyte solutions to fluorine gas. The treatment with fluorine gas will preferably be carried out by contacting the surfaces with fluorine gas at a temperature of below 50C. A fluorination process for the production of fluorinated polyethylene film and fluorinated polyethylene containers is disclosed in US-A-2811468 and a similar process may be used in the present invention.
The fluorination may be carried out using an atmosphere containing 1000 fluorine, or the fluorine may be diluted with an inert gas such as nitrogen.
When the halogenation process is a bromination process, this may be effected by exposing the surfaces -to a solution containing bromine. For example, if the cell is to be used as an electrochemical cell in-which one half of the cell uses a bromineJbromidereaction, the surfaces of the cell may effectively be treated by exposing them to the bromine containing solution before the cell is brought into operation..
It will be understoodthat those parts only of the cell structure which, in use, will be in contact with the- anolyte or catholyte need to be subjected to the halogenation process: --Thus; if a complicated cell w, structure is-being fabricated it is possible to post halogenate the cell structure in sections, ensuring that any areas of the structures which are required to be joined together or to any other elements of the cell to form the final cell structure are-not subjected to the halogenatuon process. For example, 2 ~ ~ ~ 3 6 4 PCTlGB9510U667 _ q _ certain areas of the cell structure such as the edges thereof may be masked during the halogenation process.
Alternatively, certain areas-of the cell structure such as the edges thereof may have upstands or sacrificial-beads formed thereon which can be machined off to leave exposed non-halogenated surfaces which can be readily joined to other non-halogenated surfaces by welding or the like. Components of the cell structure may thus be joined in this manner to other elements of the cell such as the cell electrodes or cellmembrane(s).
Alternatively or in addition any elements of the cell structure which would be sensitive to halogenation may be masked prior to the halogenation and the masking removed after the halogenation. For example, the electrodes may be incorporated into appropriate sections of the cell structure prior to the halogenation and masked during the halogenation process-.- The electrodes will then not be affected by the halogenation process and the sections-of the cell structure can then be joined together, or to other elements of the cell, once the masking is renoved.
The present invention also includes within its scope an electrochemical cellwhich has been prepared according to the method of the invention in which the surfaces of the cell structure which, in use,-will be in contact with the anolyte and catholyte solutions have been subjected to a post halogenation treatment to form a chemically stable halogen modified polymeric material.
The present invention will, be-further described with reference to the following Examples:
EXAMPLE 1.
One millimetre thick pieces of high density polyethylene, fluorinated high density polyethylene, WO 95!27751 218 7 3 6 4 PCTIGB95/OU667 high density polyethylene filled with titanium dioxide ' and fluorinated high density polyethylene filled with titanium dioxide were-immersed in a solution of 1.5M
' Brz/3M NaBr and the percentage changes in mass and dimensions with time were measured.
The results are given in Figures 1 to 4. Figures 1 and 2 illustrate the percentage changes in dimension and mass, respectively, for an unfluorinated high density polyethylene. It will be noted from these Figures that initially the polyethylene changed significantly in dimensions and mass as the surface of the polyethylene was brominated by the bromine containing solution. Thereafter the high density polyethylene became relatively stabilized in the solution. Figures 3 and 4 illustrate the percentage changes in-dimension and mass, respectively, for both the filled fluorinated and unfilled fluorinated high density polyethylene samples.-- Figure 4, in particular, illustrates that both the filled fluorinated and unfilled fluorinated high density polyethylene samples are stable in the Brz/NaBr solution after an initial change in mass on immersion in the solution.
~XAMPL~ 2 The permeability to bromine of high density polyethylene (HDPE) with and without a surface fluorine treatment was studied using a method which is a variation of the ASTM test method D26$4.
Polyethylene containers of 25D ml capacity were each partially filled with 200 ml of an aqueous solution of 1.5M bromine in 4M sodium bromide and the containers sealed with fluoroelastomer stoppers. The containers were then each immersed in a glass jar containing 100 ml of a 0.1M aqueous solution of sodium W095127751 ~ ~ ~ PCTlGB95/00667 _ g _ hydroxide.which was also sealed. Throughout each test the vessels were-maintained at either 21°C or 58°C by-immersion in a thermostatically controlled water bath.
At intervals the sodium hydroxide solutions were replaced and the amount of br-omine which had escaped from within each container and which had been trapped by the sodium. hydroxide solutions was determined using ion chromatography. ' This method allowed a direct comparison to be.
l0 made of bromine escape from containers which were identical, except for the surface-fluorination-treatment.
The results are shown in Figure 5 from which it can be seen that the escape of bromine from the untreated HDPE containers began almost immediately and proceeded fairly rapidly,-whilst for zhe fluorinated FL-HDPE containers the escape-ofbromine was significantly delayed and then proceeded only very slowly.
A cell according to the present invention was constructed according to the following method.
Plates of-high density polyethylene were machined in order to provide in the surface or surfaces of each plate the desired profiles to-give-desired cell design. Thus, the plates were machined to provide flow. distributors forthe-electrolytes, flow distribution channels and appropriate holes for the, electrodes:. The electrodes s~Jere then welded into holes provided.in the machined plates, masked and the plates subjected to a--fluorination treatment using fluorine gas mixed with nitrogen in accordance-with the teaching of US Patent No. 2811468.
The masking was then removed from the electrodes.
R'O 95127751 218 l 3 b 4 PCT1GB951Q0667 The fluorinated plates were then separated one from ~ another with cation exchange membranes and a plurality of the plates separated by the membranes were bolted together to form a multi-compartment cell.
. f .
Claims (11)
1. A method of fabricating an electrochemical cell which has long term chemical stability to anolyte and catholyte solutions at pH's of less than 2 and above 12, which method comprises the steps of:
i) thermally processing a polymeric material which exhibits a glass transition and/or melting thermal transition to form the cell structure or components of the cell structure, and ii) subjecting the surfaces of the cell structure or components of the cell structure which, in use, will be in contact with the anolyte and catholyte solutions, to a post halogenation process, whereby the polymeric material forming the said surfaces undergoes halogen substitution to form a chemically stable halogen modified polymeric material.
i) thermally processing a polymeric material which exhibits a glass transition and/or melting thermal transition to form the cell structure or components of the cell structure, and ii) subjecting the surfaces of the cell structure or components of the cell structure which, in use, will be in contact with the anolyte and catholyte solutions, to a post halogenation process, whereby the polymeric material forming the said surfaces undergoes halogen substitution to form a chemically stable halogen modified polymeric material.
2. A method as claimed in claim 1 wherein the polymeric material has a Newtonian melt viscosity at 150°C and 400 Pascals of less than 1000 Pascal seconds.
3. A method as claimed in claim 1 wherein the polymeric material used in step (i) is high or low density polyethylene, polypropylene or an ethylene-propylene copolymer.
4. A method as claimed in any one of the preceding claims wherein the cell structure or components of the cell structure are formed by machining of preformed sheets or plates, injection moulding, transfer moulding or compression moulding.
5. A method as claimed in any one of the preceding claims wherein the post halogenation is a fluorination process.
6. A method as claimed in claim 5 wherein the fluorination is effected by exposing the surfaces which, in use, will be in contact with the anolyte and catholyte solutions, to fluorine gas.
7. A method as claimed in claim 6 wherein the exposure to fluorine gas is carried out at a temperature of below 50°C.
8. A method as claimed in any one of claims 1 to 4 wherein the post halogenation is a bromination process.
9. A method as claimed in claim 8 wherein the bromination is carried out by exposing the surfaces which, in use, will be in contact with the anolyte solution to a bromine containing solution.
10. A method as claimed in claim 9 wherein the anolyte compartment of the cell is intended for use in a bromine/bromide reaction and the surfaces of the cell are exposed to a solution containing bromine before the cell is brought into operation.
11. An electrochemical cell which has been fabricated by a method as claimed in any one of claims 1 to 10.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9407048.9 | 1994-04-08 | ||
| GB9407048A GB9407048D0 (en) | 1994-04-08 | 1994-04-08 | Method for the fabrication of an electrochemical cell |
| PCT/GB1995/000667 WO1995027751A1 (en) | 1994-04-08 | 1995-03-24 | Method for the fabrication of an electrochemical cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2187364A1 CA2187364A1 (en) | 1995-10-19 |
| CA2187364C true CA2187364C (en) | 2004-10-26 |
Family
ID=10753279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002187364A Expired - Fee Related CA2187364C (en) | 1994-04-08 | 1995-03-24 | Method for the fabrication of an electrochemical cell |
Country Status (28)
| Country | Link |
|---|---|
| US (1) | US5785912A (en) |
| EP (1) | EP0764183B1 (en) |
| JP (1) | JPH10502206A (en) |
| KR (1) | KR100343758B1 (en) |
| CN (1) | CN1070516C (en) |
| AT (1) | ATE166663T1 (en) |
| AU (1) | AU698082B2 (en) |
| BG (1) | BG62334B1 (en) |
| BR (1) | BR9507310A (en) |
| CA (1) | CA2187364C (en) |
| CZ (1) | CZ289632B6 (en) |
| DE (1) | DE69502721T2 (en) |
| DK (1) | DK0764183T3 (en) |
| EG (1) | EG20590A (en) |
| ES (1) | ES2116739T3 (en) |
| FI (1) | FI964014A7 (en) |
| GB (1) | GB9407048D0 (en) |
| HU (1) | HU218105B (en) |
| IL (1) | IL113087A (en) |
| MY (1) | MY115348A (en) |
| NO (1) | NO315729B1 (en) |
| NZ (1) | NZ282458A (en) |
| PL (1) | PL316674A1 (en) |
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| SK (1) | SK127996A3 (en) |
| UA (1) | UA44271C2 (en) |
| WO (1) | WO1995027751A1 (en) |
| ZA (1) | ZA952292B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012048276A2 (en) | 2010-10-08 | 2012-04-12 | Caridianbct, Inc. | Customizable methods and systems of growing and harvesting cells in a hollow fiber bioreactor system |
| WO2015073913A1 (en) | 2013-11-16 | 2015-05-21 | Terumo Bct, Inc. | Expanding cells in a bioreactor |
| WO2015148704A1 (en) | 2014-03-25 | 2015-10-01 | Terumo Bct, Inc. | Passive replacement of media |
| EP3198006B1 (en) | 2014-09-26 | 2021-03-24 | Terumo BCT, Inc. | Scheduled feed |
| WO2017004592A1 (en) | 2015-07-02 | 2017-01-05 | Terumo Bct, Inc. | Cell growth with mechanical stimuli |
| US11965175B2 (en) | 2016-05-25 | 2024-04-23 | Terumo Bct, Inc. | Cell expansion |
| US11104874B2 (en) | 2016-06-07 | 2021-08-31 | Terumo Bct, Inc. | Coating a bioreactor |
| US11685883B2 (en) | 2016-06-07 | 2023-06-27 | Terumo Bct, Inc. | Methods and systems for coating a cell growth surface |
| CN117247899A (en) | 2017-03-31 | 2023-12-19 | 泰尔茂比司特公司 | cell expansion |
| US12234441B2 (en) | 2017-03-31 | 2025-02-25 | Terumo Bct, Inc. | Cell expansion |
| US11624046B2 (en) | 2017-03-31 | 2023-04-11 | Terumo Bct, Inc. | Cell expansion |
| EP4314244B1 (en) | 2021-03-23 | 2025-07-23 | Terumo BCT, Inc. | Cell capture and expansion |
| US12209689B2 (en) | 2022-02-28 | 2025-01-28 | Terumo Kabushiki Kaisha | Multiple-tube pinch valve assembly |
| USD1099116S1 (en) | 2022-09-01 | 2025-10-21 | Terumo Bct, Inc. | Display screen or portion thereof with a graphical user interface for displaying cell culture process steps and measurements of an associated bioreactor device |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2811468A (en) * | 1956-06-28 | 1957-10-29 | Shulton Inc | Impermeable polyethylene film and containers and process of making same |
| GB1024978A (en) * | 1962-07-30 | 1966-04-06 | Nat Distillers Chem Corp | Treatment of polyolefin surfaces |
| US3544383A (en) * | 1968-12-16 | 1970-12-01 | Esb Inc | Method of sealing an electric battery by means of spin welding |
| US4142032A (en) * | 1977-12-29 | 1979-02-27 | Union Carbide Corporation | Process for improving barrier properties of polymers |
| US4485154A (en) * | 1981-09-08 | 1984-11-27 | Institute Of Gas Technology | Electrically rechargeable anionically active reduction-oxidation electrical storage-supply system |
| US4454208A (en) * | 1983-03-31 | 1984-06-12 | Union Carbide Corporation | Pressure contact tab/cover construction for electrochemical cells |
| DE3435592A1 (en) * | 1984-09-28 | 1986-04-03 | Kautex Werke Reinold Hagen AG, 5300 Bonn | METHOD FOR PRODUCING HOLLOW BODIES FROM THERMOPLASTIC PLASTIC |
| DE3640975C2 (en) * | 1986-12-01 | 1994-08-11 | Messer Griesheim Gmbh | Process for the production of fluorinated surfaces of high density polyethylene (HDPE) |
| US4752540A (en) * | 1987-06-05 | 1988-06-21 | Honeywell Inc. | Polymeric enclosures for non-aqueous active metal cells |
| JPS6481802A (en) * | 1987-09-22 | 1989-03-28 | Sekisui Chemical Co Ltd | Composite pipe |
| US5401451A (en) * | 1993-07-13 | 1995-03-28 | Air Products And Chemicals, Inc. | Process for producing permeation resistant containers |
| RU2064207C1 (en) * | 1994-10-14 | 1996-07-20 | Евдокимов Анатолий Кириллович | Method of manufacture of cylindrical cans for alkaline chemical current sources |
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1994
- 1994-04-08 GB GB9407048A patent/GB9407048D0/en active Pending
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1995
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- 1995-03-22 IL IL113087A patent/IL113087A/en not_active IP Right Cessation
- 1995-03-24 DK DK95912353T patent/DK0764183T3/en active
- 1995-03-24 AT AT95912353T patent/ATE166663T1/en not_active IP Right Cessation
- 1995-03-24 ES ES95912353T patent/ES2116739T3/en not_active Expired - Lifetime
- 1995-03-24 HU HU9602752A patent/HU218105B/en not_active IP Right Cessation
- 1995-03-24 EP EP95912353A patent/EP0764183B1/en not_active Expired - Lifetime
- 1995-03-24 US US08/718,519 patent/US5785912A/en not_active Expired - Fee Related
- 1995-03-24 CZ CZ19962939A patent/CZ289632B6/en not_active IP Right Cessation
- 1995-03-24 JP JP7526145A patent/JPH10502206A/en active Pending
- 1995-03-24 BR BR9507310A patent/BR9507310A/en not_active IP Right Cessation
- 1995-03-24 PL PL95316674A patent/PL316674A1/en unknown
- 1995-03-24 SK SK1279-96A patent/SK127996A3/en unknown
- 1995-03-24 DE DE69502721T patent/DE69502721T2/en not_active Expired - Fee Related
- 1995-03-24 RU RU96121553A patent/RU2140119C1/en not_active IP Right Cessation
- 1995-03-24 CA CA002187364A patent/CA2187364C/en not_active Expired - Fee Related
- 1995-03-24 KR KR1019960705612A patent/KR100343758B1/en not_active Expired - Fee Related
- 1995-03-24 CN CN95193328A patent/CN1070516C/en not_active Expired - Fee Related
- 1995-03-24 UA UA96103831A patent/UA44271C2/en unknown
- 1995-03-24 NZ NZ282458A patent/NZ282458A/en not_active IP Right Cessation
- 1995-03-24 WO PCT/GB1995/000667 patent/WO1995027751A1/en not_active Ceased
- 1995-03-24 AU AU19565/95A patent/AU698082B2/en not_active Ceased
- 1995-03-24 FI FI964014A patent/FI964014A7/en not_active Application Discontinuation
- 1995-04-05 EG EG27195A patent/EG20590A/en active
- 1995-04-07 MY MYPI95000906A patent/MY115348A/en unknown
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