WO1997015959A1 - Procede de fabrication d'une cellule electrochimique et cellule electrochimique obtenue selon ce procede - Google Patents
Procede de fabrication d'une cellule electrochimique et cellule electrochimique obtenue selon ce procede Download PDFInfo
- Publication number
- WO1997015959A1 WO1997015959A1 PCT/CH1996/000370 CH9600370W WO9715959A1 WO 1997015959 A1 WO1997015959 A1 WO 1997015959A1 CH 9600370 W CH9600370 W CH 9600370W WO 9715959 A1 WO9715959 A1 WO 9715959A1
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- Prior art keywords
- semiconductor layer
- substrate
- layer
- cell
- polymer
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 24
- 239000004065 semiconductor Substances 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000001737 promoting effect Effects 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 3
- -1 polyethylene terephthalate Polymers 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 7
- 150000004767 nitrides Chemical class 0.000 claims description 6
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 150000004703 alkoxides Chemical class 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 claims description 3
- 229920000307 polymer substrate Polymers 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 229910000765 intermetallic Inorganic materials 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 13
- 238000007789 sealing Methods 0.000 abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 230000008569 process Effects 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- QFJIELFEXWAVLU-UHFFFAOYSA-H tetrachloroplatinum(2+) dichloride Chemical compound Cl[Pt](Cl)(Cl)(Cl)(Cl)Cl QFJIELFEXWAVLU-UHFFFAOYSA-H 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
-
- 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
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/40—Printed batteries, e.g. thin film batteries
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/50—Forming devices by joining two substrates together, e.g. lamination techniques
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar 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
- 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
Definitions
- the present invention relates to a method for manufacturing electrochemical cells, in particular photovoltaic cells, batteries or electrochromic windows, each cell comprising a working electrode, a counter electrode and an ionic or electronic conductive agent disposed between these two electrodes, in which, to form said working electrode, an electrically conductive layer and at least one nanocrystalline semiconductor layer are successively deposited on a polymer material substrate.
- an electrochemical cell in particular a photovoltaic cell, a battery or an electrochromic window comprising a substrate made of polymer material covered with a conductive layer and at least one nanocrystalline semiconductor layer.
- Electrochemical cells there are currently different types of electrochemical cells, including photovoltaic cells, batteries and electrochromic windows.
- Photovoltaic cells in particular are very interesting for applications in which the yields are not considered to be very high, while the manufacturing costs must be reduced to the minimum.
- Cells of this type are described in particular in the three international patent applications published under the numbers WO 91/16719, WO 93/18532 and WO 93/20569 and in the European patent application published under the number 0 664 570.
- the cells electrochemicals that they describe comprise a glass substrate covered with a conductive layer, or a substrate in an intrinsically conductive polymer covered with a layer of a porous semiconductor material such as anatase (Ti0 2 ).
- the sintering is carried out in six to ten decomposition cycles at 200 ° C for 30 minutes, then in a final baking at 250 ° C for one hour.
- the cooking takes place at a temperature of between 400 ° C. and 550 ° C. It is therefore necessary to use substrates resistant to these high temperatures. This is not a problem when the substrate is glass.
- the disadvantage of glass is its brittleness and its relatively high cost compared to conventional polymers.
- it is not possible to produce cells of small thickness and cutting the cells into complex shapes is particularly difficult and leads to a high rate of waste.
- Heating to a temperature as mentioned above during sintering poses serious problems when it is desired to use a polymer, since few polymers resist such temperatures. In addition, heating to a high temperature involves significant energy consumption.
- the present invention proposes to overcome these drawbacks by providing a simple deposition process allowing the use of conventional polymers, inexpensive and giving cells that are easy to cut, thus offering great freedom of shape.
- This object is achieved by a process as defined in the preamble and characterized in that it includes a step of sintering the semiconductor layer, this sintering being carried out at a temperature below 200 ° C.
- the material constituting the semiconductor layer is prepared by mixing a powder of the compounds constituting this material with water and / or a volatile organic compound having a boiling temperature below 200 °. C, and a stabilizer, so as to form a paste, this paste containing less than 5% by weight of non-volatile organic compounds.
- the semiconductor layer advantageously comprises oxide, sulfide, phosphide or nitride of an element chosen from the group formed by titanium, molybdenum, tungsten, zirconium, tantalum and niobium.
- a polymer substrate is preferably used, the maximum temperature of use of which is at least 80 ° C.
- a substrate of transparent or translucent polymer and in particular, a substrate of a polymer chosen from polyethylene terephthalate, polyethylene naphthalate, polyphenylsulfonate, polyimide, polyemylene nitride or polypropylene.
- the substrate is formed from a polymer whose maximum temperature of use is at least 80 ° C.
- This substrate is advantageously formed from a polymer chosen from polyuretylene terephthalate, polyethylene naphthalate, polyphenylsulfonate, polyimide, polyethyleneimide or polypropylene.
- the semiconductor layer is preferably formed of a porous nanocrystalline semiconductor. It is advantageously formed of a compound metallic chosen from oxides, sulfides, nitrides and phosphides of an element chosen from the group formed from titanium, molybdenum, tungsten, zirconium, tantalum and niobium.
- the cell comprises an adhesion promoting layer disposed between the conductive layer and the semiconductor layer.
- This adhesion promoting layer advantageously comprises a metal alkoxide and preferably has a thickness of between 0.5 nm and 500 nm.
- the semiconductor layer has a thickness of between 0.2 ⁇ m and 100 ⁇ m.
- FIG. 1 is a sectional view of an electrochemical cell according to the present invention.
- FIG. 2 illustrates a method of manufacturing a counter electrode for a cell according to the present invention
- FIG. 3 and 4 show two modes of assembling the electrodes of electrochemical cells according to the invention.
- the electrochemical cell 10 has a first electrode 11, called the working electrode, and a second electrode 12, called the counter electrode.
- the working electrode 11 comprises a flexible substrate 13 formed from a polymer which is preferably not intrinsically conductive.
- This polymer must have a maximum operating temperature of at least 80 ° C and can be formed from a film of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylsulfonate, polyimide, polyethyleneimide, polypropylene or a perfluorinated polymer.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- polyphenylsulfonate polyimide
- polyethyleneimide polyethyleneimide
- polypropylene polypropylene or a perfluorinated polymer.
- This film is covered with a transparent electrically conductive layer 14 containing for example indium tin oxide, doped zinc oxide or doped tin oxide.
- the working electrode may also comprise an adhesion promoting layer 15 comprising a metal oxide facilitating the attachment of upper layers to the conductive layer 14.
- this metal oxide is deposited by hydrolysis or by decomposition of a metal alkoxide in an alcoholic solution, for example a 50 mM solution of titanium isopropoxide in isopropanol.
- the electrode 11 comprises a layer 16 of a porous semiconductor material impregnated with an ionic or electronic conductive agent such as an electrolyte 17.
- This semiconductor material is an oxide, a sulfide, a phosphoride or a nitride of a compound chosen from transition metals, rare earths or the elements of columns 13 and 14 of the modern periodic table (See Cours de chimie physique de Paul Arnaud, Editions Dunod, 1988). Elements particularly well suited to this use are titanium, molybdenum, tungsten, zirconium, tantalum and niobium. This semiconductor material contains practically no non-volatile organic compounds, the percentage of these organic compounds by weight always being less than 5%.
- the counter electrode 12 is formed of a flexible substrate 18, for example also made of PET or PEN, on which are deposited a transparent conductive layer 19 and a catalyst 20.
- a sealing frame 21 made of glue is deposited on the counter -electrode so as to delimit the space occupied by the electrolyte 17.
- the substrate 18 of the counter-electrode is generally transparent or translucent.
- the manufacturing method of the present invention is described below with reference to FIGS. 2 to 4. It essentially comprises a step of manufacturing the working electrode 11, a step of manufacturing the counter-electrode, a step of impregnation of the working electrode and a cell sealing step. These steps can be followed, if necessary, by cutting the cells obtained.
- the manufacture of the working electrode 11 consists in cleaning the flexible substrate
- the conductive layer 14 of indium, tin or zinc oxide on this substrate.
- substrates covered with a conductive layer are commercially available under the name Altair- M® from the Southwall Technologies, Palo Alto, California, USA.
- the adhesion promotion layer 15 is then deposited on the conductive layer. This adhesion layer is simply dried at room temperature. A thickness of approximately 100 nm of titanium oxide is formed by hydrolysis of the titanium alkoxide at room temperature and humidity. This deposit can be repeated several times, depending on the quality and thickness desired.
- the porous layer 16 of semiconductor oxide is then deposited on the adhesion layer.
- This porous layer is deposited in the form of a paste obtained by mixing a nanocrystalline powder or a colloidal aqueous solution of the components constituting said material with water or with a mixture of water and a low-point organic vehicle. boiling, this paste containing less than 5% by weight of non-volatile organic compounds.
- organic vehicle an alcohol, a ketone, an ether or an ester or a mixture of these compounds, having a boiling point below 200 ° C.
- the most advantageous organic vehicle is an alcohol chosen from ethanol, propanol, isopropanol, tert-butanol, butanol, 2-butanol, pentanol, 2-pentanol and 3-pentanol.
- the paste is composed of nanocrystalline titanium oxide, water and / or ethanol, this paste being stabilized by an acid such as nitric acid, a volatile organic compound such as 4-hydroxy benzoic acid, a surfactant sold by the company Rohm & Haas under the name Triton X- 100® , a base such as caustic soda or an amine.
- the deposit obtained is dried, then undergoes a heat treatment such as sintering at a temperature of approximately 130 ° C for 10 minutes, in order to form a porous layer and to ensure electrical continuity between the nanocrystalline grains.
- the electrode is optionally subjected to a surface treatment making it possible to optimize the short-circuit current and the open circuit voltage.
- the electrode 11 is placed in a bath of a dye solution for a time sufficient to impregnate the sintered layer.
- the assembly is then rinsed so as to remove the residues of non-adsorbed dye, then it is dried.
- the manufacture of the counter electrode 12 begins with a step consisting in depositing, for example by sputtering, the transparent conductive layer 19, then in depositing the catalyst 20 on the flexible substrate 18. This deposit is made for example by electroplating in a bath based on platinum hexachloride.
- the sealing frame 21 is then applied by screen printing on the upper layer of the counter-electrode. In the case illustrated in FIG. 2, the electrolyte is applied in the sealing frame, by pouring from a reservoir 22.
- a scraper 23 then makes it possible to eliminate the superfluous quantity and to regulate the quantity of electrolyte. Depending on this electrolyte, it may have to be dried or reflowed.
- the assembly step is illustrated in more detail by FIGS. 3 and 4.
- the manufacturing process uses an assembly device 30 comprising two heating rollers 31, 32 allowing guidance of strips of polymers on which the electrodes are made, and which can also be used to heat these strips.
- These two rollers heat the strips and the glue of the sealing frame 21 to a temperature between 20 ° and 200 ° C and preferably between 120 ° and 150 ° C, and stick the two electrodes on top of each other.
- Two additional rollers (not shown) can also be used to lower the temperature of the strip so as to accelerate the setting of the adhesive.
- the electrolyte 17 is a pasty electrolyte.
- the sealing frame 21 is arranged so as to fill the space between two consecutive cells. This process allows the use of solid polymer electrolytes at room temperature.
- the electrolyte 17 is a liquid electrolyte introduced continuously, before the electrodes are bonded, between the two strips of substrates by a metering system 40. This process makes it possible to ensure an excess of constant electrolyte. This excess electrolyte is removed when the two electrodes arrive in the contact zone of the two heating rollers 31, 32.
- the adhesive forming the sealing frame 21 is chosen so that it can adhere to the second electrode through the liquid electrolyte.
- This sealing frame is arranged so as to form a sealed capsule when the two electrodes are glued to one another. This process allows optimal filling of the electrolyte in the cells.
- the method according to the present invention does not use any step of heating the substrate to a temperature above about 130 ° C. In this way, it is possible to use a large number of polymers as a substrate. In particular, it is possible to use particularly inexpensive materials for the production of the cells described above.
- the different methods of assembling the cells described above can also be used for the production of a hthiurn battery.
- the dye used in the photovoltaic cell is replaced by a layer of lithium and the layer forming the catalyst by a layer of a metal oxide such as vanadium pentoxide.
- the manufacturing and assembly process is the same for photovoltaic cells and for lithium batteries.
- This manufacturing method is particularly economical and suitable for the manufacture of electrochemical cells for small electrical devices. It allows easy cutting in any shape, which allows its use in all kinds of objects such as watches with dials of non-rectangular and non-circular shape.
- the manufacture of these cells can be done in a medium having normal humidity, unlike the manufacture of a large number of cells of the prior art which require the use of chambers free of humidity. It is also possible to demold the cells over a radius of between 1 and 5 cm, which allows continuous production of cells and storage in the form of coils.
- the present invention is not limited to the embodiments described, but extends to any modification obvious to those skilled in the art.
- the choice of the material constituting the substrates can be practically any.
- the electrolyte can also be a polymer which can have an adhesive function making it possible to assemble the two electrodes. In this case, it is not necessary to place a sealing frame around each cell.
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU72094/96A AU7209496A (en) | 1995-10-24 | 1996-10-22 | Method for making an electrochemical cell, and resulting electrochemical cell |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH3004/95 | 1995-10-24 | ||
CH300495 | 1995-10-24 |
Publications (1)
Publication Number | Publication Date |
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WO1997015959A1 true WO1997015959A1 (fr) | 1997-05-01 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CH1996/000370 WO1997015959A1 (fr) | 1995-10-24 | 1996-10-22 | Procede de fabrication d'une cellule electrochimique et cellule electrochimique obtenue selon ce procede |
Country Status (2)
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AU (1) | AU7209496A (fr) |
WO (1) | WO1997015959A1 (fr) |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL1009431C1 (nl) * | 1998-06-18 | 1998-12-12 | Stichting Energie | Omgekeerde kleurstof- en gesensibiliseerde foto-voltaische cel. |
WO1999038222A1 (fr) * | 1998-01-26 | 1999-07-29 | Air Products And Chemicals, Inc. | Procede et dispositif servant a creer un motif sur un clinquant metallique |
WO1999049483A1 (fr) * | 1998-03-26 | 1999-09-30 | Akzo Nobel N.V. | Procede de production d'une cellule photovoltaïque contenant un colorant |
NL1009432C2 (nl) * | 1998-06-18 | 1999-12-21 | Stichting Energie | Werkwijze voor het vervaardigen van een vloeistofhoudend foto-voltaïsch element en volgens deze werkwijze vervaardigd element. |
WO2000022682A2 (fr) * | 1998-10-09 | 2000-04-20 | The Trustees Of Columbia University In The City Of New York | Dispositif photoelectrique solide |
WO2000036666A1 (fr) * | 1998-12-15 | 2000-06-22 | E Ink Corporation | Procede d'impression d'ensembles de transistors sur des substrats en plastique |
US6183899B1 (en) * | 1997-03-13 | 2001-02-06 | Alcatel | Maintenance-free open industrial type alkaline electrolyte storage battery |
WO2001022518A1 (fr) * | 1999-09-22 | 2001-03-29 | Koninklijke Philips Electronics N.V. | Accumulateur au lithium comportant des cellules individuelles connectees entre elles, et montres, ordinateurs et equipement de communication equipes de cet accumulateur |
EP1244114A1 (fr) * | 2001-03-20 | 2002-09-25 | ILFORD Imaging Switzerland GmbH | Films électro-actifs |
US6639578B1 (en) | 1995-07-20 | 2003-10-28 | E Ink Corporation | Flexible displays |
WO2003107471A1 (fr) | 2002-06-14 | 2003-12-24 | 日立マクセル株式会社 | Transducteur photoelectrique et procede de fabrication de celui-ci |
WO2008093121A2 (fr) * | 2007-02-02 | 2008-08-07 | G24 Innovations Limited | Réseaux de cellules photovoltaïques |
US7923629B2 (en) * | 2005-12-07 | 2011-04-12 | Samsung Electronics Co., Ltd. | Method for fabricating flexible semiconductor electrode, semiconductor electrode fabricated thereby, and solar cell using the semiconductor electrode |
WO2011026812A3 (fr) * | 2009-09-02 | 2011-05-26 | Bangor University | Incorporation de platine basse température destinée à des cellules solaires à colorant |
CN102176378A (zh) * | 2011-03-04 | 2011-09-07 | 复旦大学 | 一种基于柔性衬底的固态超级电容器及其制作方法 |
US11189432B2 (en) | 2016-10-24 | 2021-11-30 | Indian Institute Of Technology, Guwahati | Microfluidic electrical energy harvester |
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US6639578B1 (en) | 1995-07-20 | 2003-10-28 | E Ink Corporation | Flexible displays |
US6183899B1 (en) * | 1997-03-13 | 2001-02-06 | Alcatel | Maintenance-free open industrial type alkaline electrolyte storage battery |
WO1999038222A1 (fr) * | 1998-01-26 | 1999-07-29 | Air Products And Chemicals, Inc. | Procede et dispositif servant a creer un motif sur un clinquant metallique |
AU741400B2 (en) * | 1998-03-26 | 2001-11-29 | Akzo Nobel N.V. | Method for making a photovoltaic cell containing a dye |
WO1999049483A1 (fr) * | 1998-03-26 | 1999-09-30 | Akzo Nobel N.V. | Procede de production d'une cellule photovoltaïque contenant un colorant |
EP0948004A1 (fr) * | 1998-03-26 | 1999-10-06 | Akzo Nobel N.V. | Procédé de fabrication d'une cellule photovoltaique contenant un colorant |
US6613598B1 (en) | 1998-03-26 | 2003-09-02 | Akzo Nobel N.V. | Method for making a photovoltaic cell containing a dye |
NL1009432C2 (nl) * | 1998-06-18 | 1999-12-21 | Stichting Energie | Werkwijze voor het vervaardigen van een vloeistofhoudend foto-voltaïsch element en volgens deze werkwijze vervaardigd element. |
WO1999066520A1 (fr) * | 1998-06-18 | 1999-12-23 | Stichting Energieonderzoek Centrum Nederland | Cellule photovoltaique inversee sensibilisee au colorant |
WO1999066519A1 (fr) * | 1998-06-18 | 1999-12-23 | Stichting Energieonderzoek Centrum Nederland | Procede de fabrication d'un element photovoltaique contenant un electrolyte liquide et element photovoltaique ainsi fabrique |
NL1009431C1 (nl) * | 1998-06-18 | 1998-12-12 | Stichting Energie | Omgekeerde kleurstof- en gesensibiliseerde foto-voltaische cel. |
US6239355B1 (en) | 1998-10-09 | 2001-05-29 | The Trustees Of Columbia University In The City Of New York | Solid-state photoelectric device |
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WO2000022682A2 (fr) * | 1998-10-09 | 2000-04-20 | The Trustees Of Columbia University In The City Of New York | Dispositif photoelectrique solide |
US6506438B2 (en) | 1998-12-15 | 2003-01-14 | E Ink Corporation | Method for printing of transistor arrays on plastic substrates |
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