CN102969167B - There is the photovoltaic dye cell of the auxiliary electrode of improvement - Google Patents
There is the photovoltaic dye cell of the auxiliary electrode of improvement Download PDFInfo
- Publication number
- CN102969167B CN102969167B CN201210365063.8A CN201210365063A CN102969167B CN 102969167 B CN102969167 B CN 102969167B CN 201210365063 A CN201210365063 A CN 201210365063A CN 102969167 B CN102969167 B CN 102969167B
- Authority
- CN
- China
- Prior art keywords
- layer
- light source
- battery
- cell
- changed
- 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.)
- Expired - Fee Related
Links
- 230000006872 improvement Effects 0.000 title description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 109
- 210000004027 cell Anatomy 0.000 claims abstract description 101
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000000975 dye Substances 0.000 claims abstract description 84
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 77
- 239000003792 electrolyte Substances 0.000 claims abstract description 55
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 52
- 239000010936 titanium Substances 0.000 claims abstract description 52
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 45
- 238000000576 coating method Methods 0.000 claims abstract description 43
- 239000011248 coating agent Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 30
- 210000002421 cell wall Anatomy 0.000 claims abstract description 15
- 230000005611 electricity Effects 0.000 claims abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 5
- 238000012546 transfer Methods 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 229910002804 graphite Inorganic materials 0.000 claims description 32
- 239000010439 graphite Substances 0.000 claims description 32
- 239000011230 binding agent Substances 0.000 claims description 27
- 239000011888 foil Substances 0.000 claims description 26
- 239000011159 matrix material Substances 0.000 claims description 13
- 230000002829 reductive effect Effects 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 8
- 239000003365 glass fiber Substances 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 149
- 239000004408 titanium dioxide Substances 0.000 abstract description 72
- 125000002346 iodo group Chemical group I* 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 163
- 239000011521 glass Substances 0.000 description 64
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 35
- 238000005245 sintering Methods 0.000 description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- 239000004020 conductor Substances 0.000 description 19
- 238000007650 screen-printing Methods 0.000 description 19
- 239000000853 adhesive Substances 0.000 description 17
- 230000001070 adhesive effect Effects 0.000 description 17
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 16
- 229910045601 alloy Inorganic materials 0.000 description 14
- 239000000956 alloy Substances 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 229910052697 platinum Inorganic materials 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 238000009413 insulation Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 239000002344 surface layer Substances 0.000 description 9
- 238000013461 design Methods 0.000 description 8
- 239000011630 iodine Substances 0.000 description 8
- 229910052740 iodine Inorganic materials 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 8
- 229910052721 tungsten Inorganic materials 0.000 description 8
- 239000010937 tungsten Substances 0.000 description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- 238000007639 printing Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 229910001887 tin oxide Inorganic materials 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910001092 metal group alloy Inorganic materials 0.000 description 5
- 230000009972 noncorrosive effect Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- -1 siloxanes Chemical class 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 229910000604 Ferrochrome Inorganic materials 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- 231100000489 sensitizer Toxicity 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000001174 ascending effect Effects 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- DKNPRRRKHAEUMW-UHFFFAOYSA-N Iodine aqueous Chemical compound [K+].I[I-]I DKNPRRRKHAEUMW-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000002547 anomalous effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 102000057593 human F8 Human genes 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002496 iodine Chemical class 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229950000845 politef Drugs 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229940020414 potassium triiodide Drugs 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229940047431 recombinate Drugs 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
- H01M14/005—Photoelectrochemical storage cells
-
- 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
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
-
- 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
- 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
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
- H10K30/83—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes comprising arrangements for extracting the current from the cell, e.g. metal finger grid systems to reduce the serial resistance of transparent electrodes
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
A kind of light source changes into the photovoltaic dye cell of electricity, including: (a) includes the room of at least partly transparent cell wall；B () is placed in electrolyte in this cell wall, containing iodo redox materials；C at least partly transparent conductive coating that () is arranged on the inner surface of this cell wall；D () is arranged on the anode on this conductive coating, and include: (i) be applicable to the porous silica titanium film being in close contact with this redox materials；(ii) absorbing the dyestuff on the surface of this porous silica titanium film, this dyestuff is applicable to film converting photons is become electronics；The negative electrode of (e) and the substantially opposite setting of this anode, and include at least one flexible conduction carbon plate being applicable to transfer an electron to the current collectingmembers relevant to this negative electrode, this conduction carbon plate is configured to communicate with the electrolysis of this porous silica titanium film via this electrolyte, wherein this conduction carbon plate forms discrete layer relative to the titanium dioxide film of this anode, and meets the profile of this film.
Description
The application is Application No. 200880113787.5, invention entitled " having the photovoltaic dye cell of the auxiliary electrode of improvement ", the divisional application of the Chinese patent application of application artificial " 3GSolar Photovoltaics Ltd. ".
Technical field
The present invention relates to produce the photovoltaic dye cell of electric energy, also referred to as DSSC from sunlight.
Background technology
The dye-sensitized photovoltaic battery of electric energy is produced by No. 5,350,644 disclosures of U.S. Patent No. of Graetzel et al. from sunlight.U.S. Patent No. 5,350,644 teaches the photovoltaic cell with the light transmissive conductive layer being deposited in glass plate or transparent polymer sheet (having applied a series of titanium dioxide layer).
U.S. Patent No. 5,350, after No. 644, the U.S. Patent No. of Kay 6,069,313 teaches the cell device of the many series connection on normal transparent substrate with that separate, parallel, narrow elongated band arrangement.Each element includes the anode towards light being made up of nano-crystalline titanium dioxide, the carbon auxiliary electrode (negative electrode) of the catalysis conductive carbon based structures of the porous that use titanium dioxide binding agent is bonded together, and place middle electric insulation porous layer based on aluminium oxide, silicon dioxide, titanium dioxide or Zirconium oxide powder to separate anode and negative electrode.With after light-sensitive coloring agent coated with nano crystal titanium dioxide, the hole in intermediate layer is at least partly filled with liquid phase, ion migration electrolyte.The current collection layer of transparent conductive material based on stannum oxide is between transparent substrates and anode.When anode is irradiated by light, anode and the negative electrode of given battery provide DC voltage so that can easily build the series component of battery.The negative electrode of each continuous elements is made to be connected with the intermediate conductive layer of anode component above by separating the gap in the respective intermediate layer of the two element.Then by organic polymer sealed cell group, specifically ensuring that the cell sealing that each single charged pool is adjacent separates, this assembly is referred to as battery black box.
Generally, above with reference to the dye cell in patent than conventional photovoltaic cell conceptually closer to battery cell, because electric charge maker is separated by an electrolyte and is not directly contacted with.These set of cells have two electrodes being separated by an electrolyte, and one of them electrode (optoelectronic pole or photo cathode) is towards the sun or light source.Each electrode supporting is on the current collector being typically electro-conductive glass sheet of himself, and this electro-conductive glass is to coat thin (～0.5 micron) on one face, be generally basede on the glass of the clear layer of conductive tin oxide.Electro-conductive glass sheet is as the transparent wall of dye cell.
Transparent polymer can be used to replace glass to support stannum oxide.Optoelectronic pole or photo cathode include the transparent porous layer of about 10 microns of thickness (contacting with stannic oxide layer) based on titanium dioxide, described titanium dioxide has the nanocrystalline characteristic particle size of 10-50nm, it is applied on electro-conductive glass or transparent polymer by baking, and impregnates specific dyestuff.Apply, with scattered form, the titanium dioxide layer that bakeed by a kind of in following various methods: scraping blade method, roll, spray, application, electrophoresis, intaglio printing, slot coated, silk screen printing or printing.Produce the baking step of the highest battery performance generally at least 450C, it is desirable to use electro-conductive glass rather than plastics to support titanium dioxide layer.Other processing procedures of titanium dioxide layer are feasible, such as, reduce baking or the compacting of temperature, and generally in efficiency, some is sacrificed.It is important to note that titanium dioxide mainly contacts with stannum oxide.Photo cathode exists other conductors (such as many metals, carbon and analog, even if being chemically inert to electrolyte) charge carrier in battery can be greatly increased recombinate and cause serious loss in efficiency.Considerably less material (the most such as stannum oxide and titanium) can be used for photo cathode, because they show chemical inertness to electrolyte, and there is no defective recombinant.
To partially transparent battery, on its respective stannum oxide sheet being coated with electro-conductive glass or transparent plastic, relative electrode (" auxiliary electrode ") includes catalyst (usual every square centimeter of platinum containing several micrograms) thin layer.If not requiring the transparency of battery, auxiliary electrode can be opaque.Such as, auxiliary electrode can be based on the carbon being advantageously catalyzed with Trace Amounts of Platinum or another kind of catalyst or graphite.Electrolyte in battery is typically the organic solvent containing the redox materials dissolved.Volatile nitrile that electrolyte is typically acetonitrile or higher molecular weight, that reduce, and redox materials is the potassium triiodide of the iodine dissolved and potassium iodide-substantially in typical battery.However, it is possible to use other solvents, salt and phase, such as substantially free of the ionic liquid of vapour pressure, even not same redox materials.
The U.S. Patent No. of Graetzel et al. 5,350,644 discloses multiple dye cell chemistry, is based especially on the dyestuff of ruthenium complex.Fall this dyestuff of the photon excitation on optoelectronic pole (generating the oxidative dye molecules of activation), causes electronics to enter in the conduction band of titanium dioxide and flow to (via having loaded external circuit) auxiliary electrode.There, the teriodide in electrolyte is reduced into iodine by electronics, and at photo cathode, the dye oxidation that this iodine is activated returns to teriodide, leaves the inactive dye molecule for next photon.U.S. Patent No. 5,350, No. 644 disclose such dye cell and can reach the electricity conversion of 10%, and obtain the efficiency more than 11% in small-sized outstanding research battery.
The electro-conductive glass (outside electro-conductive glass highlights binding agent on each face, it is allowed to current draw) that the battery of the U.S. Patent No. of Graetzel et al. 5,350,644 seals with organic bond in edge based on two panels.Under peak value shines upon, these batteries voltage with about 700mV and the current density operation of 15mA/sq.cm, and auxiliary electrode is positive pole.This patent is thought and is low cost due to material and preparation method and titanium dioxide layer can large area be prepared, so such battery may provide the good approach of low cost photovoltaic cell potentially.This patent advocate further likely than traditional monocrystalline or polycrystal silicon cell and even closer to film photovoltaic cell there is significant cost saving, because these are all high costs and depend on costliness and often cause the raw material of environmental problem, and the semi-conductor industry process equipment of complex and expensive and production technology.These shortcomings include using vacuum moulding machine and semiconductor doping methods, toilet's scheme, use poisonous hydride such as silane, hydrogen phosphide etc. as raw material, and use comprises the toxic active layer material of cadmium, selenium or tellurium.
It is the subject matter of dye cell via the ohmic loss of the electro-conductive glass coated with stannum oxide.Doped tin oxide coatings is very thin, and thickness is typically limited to less than 1 micron, because high light must be kept to be transmitted through photo cathode dyestuff/titanium dioxide layer.And, stannum oxide is only semiconductive, has about 5x10-4The resistivity of ohmcm, further, it is difficult to cohesive ground bonding.Therefore, in such battery design, the most undersized battery or there is the charged pool of long and narrow active titanic dioxide band greatly limit current draw.
It should be pointed out that, that active zone battery has some technology inferior position.Such as, in the battery of above-mentioned Kay, owing to ohmic loss limits, titanium dioxide band and corresponding carbon ribbon are the narrowest (typically only having 6-8mm width).Which results in the excessive loss of active area between the battery configuration and battery that electric current limits, the loss of the latter seals the developed width of the inert material needed owing to intercell.Under any circumstance, sufficiently seal effectively to prevent any intercell electrolyte to be still stern challenge between adjacent battery.
Make efforts and brought active area and the width of increase battery by setting level capable conduction on conductive glass surface upper berth, be achieved in large area, wide battery configuration.The U.S. Patent No. of Kurth 6,462,266 discloses the photovoltaic cell of a kind of conductive strips having and being arranged on that separate, glass support pane.Print in slurry form based on silver or the conductive strips of silver alloy, copper or copper alloy, burn till the most at elevated temperatures.Thinking prevents these conductive strips from being corroded by cell electrolyte by the insulating coating being made up of the glass of heavy metal free.
U.S. Patent No. 5 relative to Graetzel et al., 350, battery disclosed in No. 644, U.S. Patent No. 6,462, the photovoltaic cell of No. 266 teachings has the ohmic loss of reduction, because conductor band is good conductor (such as silver slurry silk screen printing and burning till at 600 DEG C), and because adds the overall effective thickness of conductive material.But, the high disposal temperature needed for silver and glaze compositions adversely affects the conductivity of doped tin oxide coatings and the long-term strength characteristic of glass.The most manageable frit material is available, but containing poisonous heavy metal such as lead, and be likely to maybe to be polluted electrolyte by the erosion of electrolyte.Additionally, be inappropriate in time by glassy layer protection silver conductor, because glaze can not get rid of aperture, especially in large-scale production process completely.It is true that the silver exposed is by the iodine fast erosion in cell electrolyte, this adversely reduces the iodine total amount in battery and irreversibly corrodes dyestuff, the deterioration being similar in the silver wire protected by polymer.
The U.S. Patent Application Publication of Goldstein the 20050072458th describes the large area for dye cell, wide electro-conductive glass or conductive plastics.This electro-conductive glass or conductive plastics carry one group of conductor selected from the material substantially preventing corrosion and carrier restructuring in the presence of cell electrolyte, and at the upper deposition of titanium oxide of this good glass or plastics (there is the electric current collection performance of enhancing than common electro-conductive glass or plastics).By example, is first slotted in electro-conductive glass face, form the shallow grooves of one group of parallel interval.Place such as titanium, molybdenum, tungsten, the metal wire of chromium or their alloy (substantially inertia of under cell operating condition, corrosion and carrier being recombinated) in each recess, and use the thermosetting adhesive slurry mixed with inertia conductive filler (such as titanium nitride) based on inactive ceramic binding agent (such as aluminium oxide) acquisition conductivity online and between stannic oxide layer on each of groove.Filled therewith groove also overlaps on each of groove, so after solidification, forms good electrical contact with stannic oxide layer.Line notch end at the glass edge of battery is prominent and can be soldered to electric current collection band.
One group of parallel metal being electroplated onto on electro-conductive glass or conductive plastics surface or metal alloy band is described in single embodiment.Under the corrosive operating condition of extreme of battery, plating alloy prevents corrosion.One example of the plated metal be given is chromium.The electric current extracted from positive plate is generated by the side of battery again, and wherein plating tape sealingly extends through the edge seal of battery.
In the further embodiment of published application, parallel conductor is inert titanium, molybdenum, tungsten, chromium or the band of their alloy or line.These firm conductors are bonded directly to the conductive surface of glass by using inertia, conductivity ceramics binding agent.
Line in No. 20050072458 electro-conductive glass extending the trough of belt being also used in battery auxiliary electrode of U.S. Patent Application Publication or the use of band being electroplated onto on electro-conductive glass.The conductive glass plate of the plating tape being provided with on bonding line in a groove or conductive surface is used as the substrate (base) of the wide negative electrode in dye cell, and uses Catalytic Layer electroactive to iodine to cover the plate that conductivity increases.The wide dye cell of each limit at least 10-15cm is possibly realized.But, although such negative electrode is provided with the suitable electric installation for extracting electric current from large-area wide battery, but forcing and need the second conductive glass layer in the battery, this is with the unfavorable result of relevant cost, weight and thickness.
The existence of the current-carrying electrodes of two physical separation may cause extra problem in the battery.Have between the electrode of so area battery of the electrode at interval and be difficult to ensure that tight and homogeneous spacing (and uniform current distribution thus).Similarly, since Full daylight is to the thermal cycle between evening (or severe cold) condition, between the electrode of cell sealing, spacing and stress are it may happen that ANOMALOUS VARIATIONS, especially true for having the cell electrolyte of notable vapour pressure.
Up to the present, photovoltaic dye cell does not has real commercialization, although it has huge Technological Economy potential.Remaining subject matter includes that width is much larger than one centimetre, the scale of the area battery much larger than 50 square centimeters.It is additionally, since the excessive ohmic loss of stannum oxide from the poor electric conductivity on glass or plastics, the long-time stability of the money base conductor in battery, and sealed cell to be dried and the difficulty of performance degradation so that opposing is long-term.Many methods depend on the internal coat by the transparent substrates of conductive tin oxide of costliness rather than use commercially available block electro-conductive glass, such as Fluorin doped zinc oxide (FTO) glass.
Excessive surface area is wasted on sealing, protective layer and conductive path on dye cell in the prior art and the sunny slope that further problem is that battery or module of module.In these cases, activated currents produces 70% that region is typically less than the geometric area (area occupied (footprint)) of battery or module, causes the effective efficiency of difference in available area.
Another problem of battery of the prior art be the wide battery to industrial applicability of (especially when auxiliary electrode is and during the separate individual component of anode) interval relatively large between anode and negative electrode-in some cases reach 100 microns-which results in the excessive ohmic loss from electrolyte.Should substantially be learnt by foregoing teachings, when auxiliary electrode is individual component separate with anode in the battery, auxiliary electrode usually requires that and uses the second glass support in the battery, or more adversely, uses the second electro-conductive glass in the battery.These substantially increase the cost of battery, weight and thickness.
Summary of the invention
According to the teachings of the present invention, it is provided that light source is changed into the photovoltaic dye cell of electricity by a kind of ohmic loss to reduce, and described battery includes: (a) room, and described room is applicable to surround described photovoltaic cell, and described room includes at least partly transparent cell wall；B () electrolyte, described electrolyte is placed in described cell wall, and described electrolyte contains iodo redox materials；C conductive coating that () is at least partly transparent, described conductive coating is arranged on the inner surface of wall；D () anode, described anode is arranged on described conductive coating, and described anode includes: (i) porous silica titanium film, and it is applicable to be in close contact with described redox materials；(ii) dyestuff, it is absorbed on the surface of described porous silica titanium film, and described dyestuff is applicable to converting photons is become electronics with described film；(e) negative electrode, described negative electrode and the substantially opposite setting of described anode, described negative electrode includes the conductive carbon layer being applicable to transfer an electron to the current collectingmembers relevant to described negative electrode, described conductive carbon layer is configured to communicate with the electrolysis of described porous silica titanium film via described electrolyte, described negative electrode has in the way of relative to the surface direct neighbor of titanium dioxide film the surface arranged, and the average distance between the described surface of the surface of wherein said negative electrode and described porous silica titanium film is less than 7 microns.
According to another aspect of the present invention, provide a kind of ohmic loss to reduce and light source is changed into the photovoltaic dye cell of electricity, described battery includes: (a) room, and described room is applicable to surround described photovoltaic cell, and described room includes at least partly transparent cell wall with inner surface；B () electrolyte, described electrolyte is placed in described cell wall, and described electrolyte contains iodo redox materials；C conductive coating that () is at least partly transparent, described conductive coating is arranged on the described inner surface of described cell wall in described photovoltaic cell；D () anode, described anode is arranged on described conductive coating, and described anode includes: (i) porous silica titanium film, and it is applicable to be in close contact with described redox materials；(ii) dyestuff, it is absorbed on the surface of described porous silica titanium film, and described dyestuff is applicable to converting photons is become electronics with described film；(e) negative electrode, described negative electrode and the substantially opposite setting of described anode, described negative electrode includes at least one flexible conduction carbon plate being applicable to transfer an electron to the current collectingmembers relevant to described negative electrode, described conduction carbon plate is configured to communicate with the electrolysis of described porous silica titanium film via described electrolyte, described conduction carbon plate forms discrete layer relative to the described porous silica titanium film of described anode, and the conduction carbon plate of wherein said flexibility meets the profile of described porous silica titanium film.
According to a further aspect of the invention, it is provided that light source is changed into the photovoltaic dye cell of electricity by a kind of ohmic loss to reduce, and described battery includes: (a) room, and described room is applicable to surround described photovoltaic cell, and described room includes at least partly transparent cell wall；B () electrolyte, described electrolyte is placed in described cell wall, and described electrolyte contains iodo redox materials；C conductive coating that () is at least partly transparent, described conductive coating is arranged on the described inner surface of described cell wall in described photovoltaic cell；D () anode, described anode is arranged on described conductive coating, and described anode includes: (i) porous silica titanium film, and it is applicable to be in close contact with described redox materials；(ii) dyestuff, it is absorbed on the surface of described porous silica titanium film, and described dyestuff is applicable to converting photons is become electronics with described film；E () current collectingmembers, it is arranged on described indoor；(f) negative electrode, described negative electrode and the substantially opposite setting of described anode, described negative electrode includes that at least one is applicable to transfer an electron to the conduction carbon plate (or carbon-coating) of described current collectingmembers, described conduction carbon plate is configured to communicate with the electrolysis of described porous silica titanium film via described electrolyte, and wherein said current collectingmembers includes that the another kind that graphite foil or thin slice or the conductive material by the ratio resistivity having less than 1200 μ Ω cm are formed is chemically inert, the paper tinsel of conduction or thin slice, they substantially be arranged in parallel with described conductive carbon sheet, described graphite foil is for from described cathode collector electric current.
According to the further feature in the preferred embodiment described, this negative electrode also include with this conductive carbon layer about and be applicable to be catalyzed the catalyst component of redox reaction of this redox materials.
According to the further feature in the preferred embodiment described, higher than at least 80%, at least 85%, at least 90% or at least 95% this distance of acquisition of this battery table area.
According to the further feature in the preferred embodiment described, the average distance between this cathode surface and porous silica titanium film surface is less than 5 microns, or even less than 3 microns.
According to the further feature in the preferred embodiment described, this negative electrode directly contacts with the surface of this porous silica titanium film.
According to the further feature in the preferred embodiment described, this photovoltaic cell also includes: metal tape that (f) at least one is relevant to this anode and this conductive coating electricity or line, and this band or line have enough thickness with the projection being formed in the plane of porous silica titanium film prominent at least 50 microns.
According to the further feature in the preferred embodiment described, this conductive carbon layer forms the sheet of at least one self-supporting.
According to the further feature in the preferred embodiment described, the sheet of this self-supporting is the most relevant to the porous silica titanium film of this anode.
According to the further feature in the preferred embodiment described, the area occupied of the single battery of this photovoltaic cell is limited by the length and width of this single battery, and wherein length and width is above 5 centimetres, and in some cases, at least 8 centimetres, or even at least 10 centimetres.
According to the further feature in the preferred embodiment described, this at least one metal tape or line are many lines, and this projection is multiple projections.
According to the further feature in the preferred embodiment described, this conductive carbon layer forms multiple self-supporting bands, and this band is placed between this projection.
According to the further feature in the preferred embodiment described, wherein the surface of this conductive carbon layer of chien shih that this band is placed in projection is substantially parallel with the surface of this porous silica titanium film.
According to the further feature in the preferred embodiment described, this conductive carbon layer is placed in porous support matrix.
According to the further feature in the preferred embodiment described, this conductive carbon layer is supported by the flexible porous support matrix being arranged between conductive carbon layer.
Porous support matrix according to the further feature in the preferred embodiment described, this conductive carbon layer and this flexibility meets the profile of this porous silica titanium film.
According to the further feature in the preferred embodiment described, the surface of this negative electrode includes the catalyst component being applicable to be catalyzed the redox reaction of this redox materials.
According to the further feature in the preferred embodiment described, the porous support matrix of this flexibility includes fiber mat.
According to the further feature in the preferred embodiment described, the porous support matrix of this flexibility includes glass fibre.
According to the further feature in the preferred embodiment described, the porous support matrix of this flexibility includes fiberglass packing.
According to the further feature in the preferred embodiment described, this conductive carbon layer includes the glass fiber tape of impregnated carbon.
According to the further feature in the preferred embodiment described, the glass fiber tape of this impregnated carbon directly contacts with the surface of this porous silica titanium film.
According to the further feature in the preferred embodiment described, this partially transparent conductive coating is stannum oxide.
According to the further feature in the preferred embodiment described, this photovoltaic cell also includes the structural element of at least one conduction relevant with conductive carbon layer, this structural element has the ratio resistivity less than 1200 μ Ω cm, and these parts are applicable to and are arranged to from cathode collector electric current.
According to the further feature in the preferred embodiment described, these electrically conductive structural parts include graphite.
According to the further feature in the preferred embodiment described, these electrically conductive structural parts include graphite foil.
According to the further feature in the preferred embodiment described, this photovoltaic cell also includes the metallic conductive element being connected with this graphite foil, and this metallic conductive element extends through the sidewall of this battery to affect current draw.
According to the further feature in the preferred embodiment described, this metallic conductive element is metal forming or wire netting.
According to the further feature in the preferred embodiment described, place between this anode and this negative electrode less than 50%, less than 30%, less than 20% or even less than 10% electrolyte.
According to the further feature in the preferred embodiment described, the conduction carbon plate of this flexibility has less than 90, less than 80 or the Shore D hardness of even below 70.
According to the further feature in the preferred embodiment described, this current collectingmembers contains the binding agent being less than 2% by weight.Preferably, this current collectingmembers contains the binding agent being less than 1% by weight, and is less than the binding agent of 0.5% the most by weight.This current collectingmembers can be substantially free of binding agent.
According to the further feature in the preferred embodiment described, this photovoltaic cell also includes the metallic conductive element being connected with graphite foil, and this metallic conductive element extends through the sidewall of this battery to affect current draw.
According to the further feature in the preferred embodiment described, this metallic conductive element is metal forming or wire netting.
The photovoltaic dye cell of the present invention can be simple, wide, large-area, efficient, low cost, light and firm, it is possible to successfully solves multiple shortcoming of the prior art.
Accompanying drawing explanation
The present invention is only described herein by embodiment with reference to accompanying drawing.Now in detail with specific reference to accompanying drawing, it is emphasised that shown special case is only used as embodiment, and be only used as the purpose of the exemplary references of the preferred embodiment for the present invention, and it be to provide for being considered as the principle of the invention and the description most useful and easy to understand of concept aspect and present.In this regard, being not intended to the ratio CONSTRUCTED SPECIFICATION showing the present invention necessary to the basic comprehension present invention in more detail, description taken together with the accompanying drawings makes the actual several forms embodying the present invention be obvious to one skilled in the art.In all of the figs, the symbol of same reference is used to specify identical element.
In the accompanying drawings:
Fig. 1 is according to the schematic cross section of a preferred embodiment of the present invention " open type " photovoltaic dye cell；
Fig. 2 provides the schematic cross section of the dye cell according to another preferred embodiment of the present invention；
Fig. 3 a provides the schematic cross section of the Promethean photovoltaic dye cell with double plate structure；
Fig. 3 b is the schematic plan of the battery of Fig. 3 a, it is shown that the setting of the anchor point of this battery；
Fig. 4 is the schematic cross section of the photovoltaic dye cell with double plate structure according to another preferred embodiment of the present invention；And
Fig. 5 provides a kind of schematic cross section with the photovoltaic dye cell with the groove filling conductor as cathode current means of delivery.
Specific embodiment
It is referred to accompanying drawing and adjoint description is more fully understood that the auxiliary electrode of the present invention and the principle of photovoltaic dye cell and operation.
Before at least one embodiment explaining the present invention, it will be appreciated that the present invention is not limited to CONSTRUCTED SPECIFICATION that is that propose in the following description or that explain in the accompanying drawings in it is applied and parts are arranged.The present invention can be other embodiment or can operate in many ways or implement.Likewise, it should be understood that wording used herein and term are as the purpose described, should not be considered as limiting.
One aspect of the present invention is the auxiliary electrode of the single dye cell wide, large-area being typically 15cm for every limit, and comprises the Promethean photovoltaic cell structure of such auxiliary electrode.We have found that when (the patent citing such as above referenced Kay of common carbon based compositions with auxiliary electrode of the prior art attempted by this kind of wide, single battery assembly, this patent uses titania powder to bond carbon-coating as binding agent) time, in addition to the prospective current of the cell widths much larger than 1cm extracts and limits, have also appeared because of additional problem produced by the most crisp character of carbon-coating.It is extremely difficult for embedding (being even partially embedded into) such as wire netting, metal forming or the current collection structure of metal wire in large-area carbon-coating and not causing total layering.This is mainly due to inorganic binder such as the inelastic nature of the titanium dioxide for the carbon-coating that bonds.Owing to the anode layer in battery and cathode layer are required for the high sintering temperature of 450C, so being often unsuitable for more flexible organic type binding agent in this applications.High sintering temperature may destroy the residual contaminants battery of organic binder bond possibility organic decomposition.Additionally, under dye cell working condition, many metals are corroded by cell electrolyte, and thus are not suitable for being used as current collector in auxiliary electrode.In the dyestuff-battery technology of Kay teaching, due to the narrow width of charged pool, these problems do not occur.In such narrow battery:
The carbon-coating of sintered (sintered-on) can show enough mechanical stabilities, and
Carbon-coating can individually carry electric current, without the current collector of auxiliary.
The battery structure of the present invention can include graphite foil, it combines the current draw element (currenttakeoffelement) of the non-corrosive metal (NCM) at least partially embedded graphite foil or metal alloy, wherein it is bonded to following negative electrode carbon-coating, or directly conductive contact structural conductive.This structure is acceptable firm and allows large area, wide battery configuration, is no longer necessary to the second conductive glass layer or the second physically separated auxiliary electrode in dye cell simultaneously.Embed the extraction element of the protection current in graphite foil and be selected from various shape, including copper, tungsten, the high-quality alloy of siderochrome or the paper tinsel of many metal or alloy, net, band or the line of the high-quality alloy of siderochrome molybdenum of such as titanium, titanium cladding.
In another one preferred implementation, non-corrosive metal (NCM) or metal alloy current draw element can be used as independent auxiliary electrode and in the battery without combining carbon or graphite layers of foil, in this case, and the auxiliary electrode being directly catalyzed with Trace Amounts of Platinum.
Fig. 1 shows the schematic cross-sectional view of an embodiment of Promethean photovoltaic dye cell 100, and this battery can be a kind of " open type " sandwich-like pattern.It is 1mm-3mm in the support glass anode-supported glass 102(typical thickness as conventional) on, it being provided with thin, transparent conductive surface layer 104, this layer is based on such as stannum oxide.Support glass 102 and conductive surface layer 104 can be provided with conductivity Enhanced feature (described in the most above referenced U.S. Patent Application Publication No. 20050072458, this patent is incorporated herein by reference based on whole purposes, just looks like that they are by the openest).Support glass 102 is used as the substrate of this dye cell and basic ingredient.This substrate is slotted and is provided with such as the line current extraction element of teaching in above referenced patent disclosure.Thus, line passes battery hermetically by the side of battery, and combines and/or by being such as welded to connect to electric current collection band (not shown), in order to form galvanic anode binding post.Applying inert, the adhesive composition 112 of conduction in each groove 108, line 116 is connected in groove by said composition 112, and makes have good bridging electrical contact on each of this groove with stannic oxide layer.As an embodiment, titanium, tungsten or high-quality alloy wire can be inserted in groove.The conductive adhesive preferably including the conductor such as titanium nitride and the binding agent such as aluminium oxide can also be added in groove.Generally by the silk screen printing of slurry, then it is dried and sintering to apply nano-crystalline titanium dioxide layer at tin oxide surface.
Porous sintered nanocrystalline titanium dioxide film or layer 120 are designed to have the typical thickness of about 15 microns.If titanium dioxide film or layer 120 can include dried layer titanium dioxide subgrade, each subgrade can silk screen printing and sintering by oneself.We have found that before applying nano-crystalline titanium dioxide layer, the upper surface covering conductive adhesive 112 with insulating barrier 124 can help to eliminate the possible short circuit occurred between anode and negative electrode.Wherein conductive adhesive surface as shown in Figure 1 may be even more important by insulating barrier 124 far above the battery of sintered titanium dioxide layer 120.
Insulating barrier 124 is selected from glaze or the adhesive composition of the most coarse titanium dioxide, zirconium oxide, aluminium oxide or the silica dioxide granule containing the characteristic particle size preferably with a few micron number magnitude, or selectively, selected from high temperature polymer such as polyimides or siloxanes.The porous insulation wall of the silk screen printing that can be used to the slurry from titanium dioxide, zirconium dioxide, silicon dioxide or alumina particle containing relative coarseness subsequently covers titanium dioxide layer 120.The wall of design silk screen printing is to generate the sintering insulated wall 128 that thickness is about 5 microns.Sintering insulated wall 128 also functions to the effect of light scattering layer, and direct light returns to sinter nano-crystalline titanium dioxide layer 120.
First pass through silk screen printing application auxiliary electrode layer to continue to construct battery.Wall 128 can be narrow, and generally in 2-10 micron number magnitude, to guarantee anode/cathode interval the least in battery, low ohmage and high battery fill factor, curve factor, all these both contributing to strengthens battery performance.Dielectric spacer layer 128 can apply thin porous carbon layer, the porous carbon layer being optionally catalyzed by Trace Amounts of Platinum or platinum catalyst substitute via the screen printing slurry containing inert binder.It is dried and sinters this thin layer to produce the sintered porous catalysis carbon-coating 132 only having a few micrometer features thickness.
It is to apply the porous, electrically conductive carbon-coating of relative thick via the screen printing carbon pastes containing inert binder after screen printing porous catalytic carbon pastes layer sintering.Carrying out another sintering step, this produces sintered porous conductive carbon layer 136.Typically design the silk screen printing of this carbon pastes so that the thickness of the conductive carbon layer 136 sintered is typically about 50-100 micron.
Conductive carbon layer 136 redox reaction to iodine in the battery can be enough activity so that can get rid of the needs that the Catalytic Layer separated such as is catalyzed carbon-coating 132.
In one preferred embodiment, if possible in single sintering step, each layer can be sintered at 450 DEG C, after Local cooling, introduce in titanium dioxide layer 120 via 136 sensitiser dye of porous carbon layer.Can have piece of graphite paper tinsel 140 that prepare, sintered, porous, conductive carbon (with chemically inert) adhesive layer 144 be placed in being provided with under it on carbon-coating 136, in order to form good conductive contact with carbon-coating 136.
Porous carbon layer 136, graphite foil 140(include adhesive layer 144) and optional Catalytic Layer 132 can form negative electrode or the auxiliary electrode 160 of battery 100.
In line, net, can be at least partially embedded in graphite foil with, the band bored a hole or the non-corrosive metal (NCM) of paper tinsel form or metal alloy current collector 152, this current collector 152 projects through the battery seal (described below) of periphery using the auxiliary electrode binding post as battery.We have found that under normal battery operational circumstances, the copper of titanium, titanium cladding and tungsten and some high-quality alloys being mainly made up of ferrochrome or ferrochrome molybdenum can be used as the current collection material of chemically stable auxiliary electrode.
Graphite foil 140 can be advantageously configured with one or more perforation 146 beneficially to make electrolyte distribution enter battery in padding subsequently.
Sheet (sheet) 154 can be arranged on the top of assembly with enclosed cell.Sheet 154 can be made up of cheap glass pane or various metals or alloy.Can be advantageously provided flexure strip 148 at the top of sheet 154 times and graphite foil 140, flexure strip 148 preferably includes foam, fiber mat or elastomeric pad or expands precursor material or expansile polymeric material or be made up of these materials.Can include that the flexure strip 148 of polymer, carbon or metal material is compressible and as spring, to help keeping relatively uniform pressure between graphite foil 140 and carbon-coating 136, on big necessary area, guarantee that enough electrical contacts are without deviating from layer 136 simultaneously.
The edge of battery 100 can be sealed by peripheral seal 156, such as, use liquid phase sealant.Electrolyte can be subsequently introduced in battery 100, typically uses vacuum mode via the hole (not shown) on sheet 154, and this hole can use sealing compositions to seal.Battery is subsequently used in test/modularity.
Fig. 2 shows the schematic cross section of the photovoltaic dye cell 200 according to another preferred embodiment of the present invention.Support that glass 202(typical thickness is 1mm-3mm in support glass such as conventional anode) on, it being provided with thin, transparent conductive surface layer 204, this layer is based on such as stannum oxide.Can be provided with the support glass 202 of conductivity Enhanced feature as the substrate of dye cell 200 and basic ingredient.Conductive surface layer 204 arranges one group of that separate, the most parallel inert metal or alloy band 216 of recombinating cell electrolyte and charge carrier.Current-delivery devices can be provided for battery 200 by the band 216 that plating mode deposits.With 216 sealably through the side of battery 200, it is possible to be electrically connected, such as, by the electric current collection band (not shown) outside sealing member, it is consequently formed the anode terminal of battery.Substantially as being described above for the groove of filling shown in Fig. 1, the band of plating can also advantageously be coated with insulating layer coating 228, such as, include that the glaze of titanium dioxide, zirconium oxide, aluminium oxide and/or silicon dioxide or adhesive composition are to prevent the short circuit of anode/anode.Generally by screen printing sizing agent, it is dried and sinters nano-crystalline titanium dioxide layer is applied on conductive surface layer 204.
The sintering nanocrystalline titanium dioxide film of porous or layer 220 are designed to have the typical thickness of about 15 microns.Titanium dioxide film or layer 220 can include some titanium dioxide subgrades, and each subgrade can silk screen printing and sintering by oneself.
Then covering titanium dioxide layer 220 with the porous insulation wall of silk screen printing, this wall experience sintering is to generate sintering insulated wall 228.The slurry of this silk screen printing can contain the titanium dioxide of relative coarseness, zirconium oxide, silicon dioxide and/or alumina particle.It is dried and after sintering, sintering insulated wall 228 can have the thickness of about 2-10 micron.Design this thickness to guarantee anode/cathode interval the least in battery.This thickness of design is to obtain low internal resistance and high battery fill factor, curve factor further, thus improves battery performance.Wall 228 also functions to the effect of light back-scattering layer, and direct light returns to sinter nano-crystalline titanium dioxide layer 220.
Dielectric spacer layer 228 arranges negative electrode or the auxiliary electrode 260 of battery 200.Negative electrode 260 includes sintered porous catalysis conductive carbon layer 232, and this carbon-coating 232 can contain the composition to battery 200 and be chemically inert binding agent and can be catalyzed by Trace Amounts of Platinum or platinum catalyst substitute.Can by silk screen printing or otherwise apply porous catalytic carbon pastes thin layer prepare carbon-coating 232, be subsequently dried and sinter this layer.Sintered porous conductive carbon layer 232 can have the thickness of several microns, typically less than about 10 microns.Arranging the sintering conductive carbon layer 236 of relative thick on catalysis carbon-coating 232, this carbon-coating 236 also can form a part for negative electrode 260.Carbon-coating 236 can be prepared by silk screen printing, be subsequently dried and sinter this layer to obtain the typical thickness of 50-100 micron.
Some high surface area carbon and graphite are so active so that can get rid of the catalysis separated or the needs of the layer 228 of platinum plating to the redox reaction of iodine in the battery.
In a preferred embodiment, typically or preferably at 450 DEG C, single sintering step sinters each layer, after Local cooling, introduce in titanium dioxide layer 220 via 236 sensitiser dye of porous carbon layer.Then, via conductive carbon tack coat 245, piece of graphite paper tinsel 240 being electrically bonded to carbon-coating 236, it is curable that this tack coat 245 can be selected at a temperature of 120 DEG C, thus avoids the heat sensitive dye in titanium dioxide layer 220 is caused any infringement.The suitable component of tack coat 245 can include carbon dust and inertia (relative to electrolyte) inorganic binder based on aluminium oxide or inertia based on such as siloxanes or polyimides (relative to electrolyte) organic binder bond.
Can consider to form graphite foil 240 and conductive carbon tack coat 245 part for negative electrode 260.
In line, net, can embed in (at least in part) graphite foil 240 with, the band bored a hole or the non-corrosive metal (NCM) of paper tinsel form or metal alloy current collector 252, this current collector 252 projects through the battery seal (described below) of periphery using the auxiliary electrode binding post as battery 200.We have found that copper and tungsten that titanium, titanium be coated with and some high-quality alloys being mainly made up of ferrochrome or ferrochrome molybdenum can be used as the current collection material of chemically stable auxiliary electrode.Graphite foil 240 can advantageously have perforation 246 so that beneficially electrolyte distribution enters battery in.Electrolyte filling step can be carried out in this stage.
From structure, battery is completed by placing piece of plastic stratiform paper tinsel 258 and apply periphery sealant 252 between the element 202 and 258 of battery, or selectively, sprayable polymeric sealing layer is first to seal this battery and using external metallization paper tinsel (not shown) to provide extra sealing.But, if light weight construction is not particularly critical, then glass pane or metal/alloy sheet may be used for this battery airtight, and in the case of the latter, can omit current collector 252.
Limit as it was previously stated, the dye cell large-area, wide with the anode physically separated and auxiliary electrode may stand various distinctive performance.A purpose that this physical separation be open type sandwich-like design as illustrated in fig. 1 and 2 is reduced or eliminated, and the most all of active layer is all glued to individually (conduct electricity) on sheet glass.In the commercial Application of wide battery, in the battery especially with non-volatile electrolyte, interelectrode spacing tends at least 50-100 micron, and at this point, the ohmic loss of cell electrolyte becomes excessive.Similarly, the variations in temperature between evening on daytime may cause the expansion/contraction change of spacing between electrode, and this may cause electric current irregular and be stressed at sealing.
But, in one preferred embodiment, we disclosing a kind of photovoltaic dye cell with the design of double plate, this photovoltaic dye cell can overcome these to limit.
Although the multiple sandwich being printed with carbon-coating on the zirconium oxide wall on titanium dioxide layer can allow the tight spacing of carbon and titanium dioxide surface, it must be stressed that such structure easily makes carbon printing layer penetrate into conductive glass surface via any hole in titanium dioxide or interval printing layer or defect.Carbon printing layer penetrates into the conductive surface of FTO glass and causes this battery short circuit, thus reduces or limits battery performance.In view of the life-span of at least 7-10 reached for battery required for commercial viability, this problem is the most serious.The Promethean double plate structure being described herein as eliminates this important and potential key issue, because carbon auxiliary electrode is not sintered (such as, at high temperature chemical bonding) to titanium dioxide or interval printing layer.On the contrary, carbon auxiliary electrode is placed in the top of wall and with physical contact wall, or can be placed in the upper surface of titanium dioxide layer, but chemical bonding is not to the different He independent entity on wall or titanium dioxide layer, as in printing carbon-coating technology.
As used in book described herein as and subsequent claim part, relative to surface and the surface (the porous silica titanium film of the carbon surface of such as negative electrode or the carbon surface of catalysis and anode) of anode of negative electrode, term " direct neighbor " refers to the surface not separated by intercalation.
As used in book described herein as and subsequent claim part, relative to cathode layer and/or anode layer, term " be the most physically correlated with " that refer to contact but un-sintered together and otherwise by chemically separated layer.
As used in book described herein as and subsequent claim part, relative to the band of negative electrode or layer and/or the layer of anode, term " self-supporting " refers to band or layer and keeps appropriate location in the battery about relative electrode with isolating construction.
As used in book described herein as and subsequent claim part, the layer adjacent relative in battery, term " discrete " refers to contact with each other but the most different layers.
Fig. 3 a provides the schematic cross section of an embodiment of the most Promethean photovoltaic dye cell 300.The anode glass 302 of the typical thickness with 1mm-3mm has thin, transparent conductive surface layer 304 based on conductive material such as stannum oxide.Anode glass 302 and conductive surface layer 304 can be provided with the feature that conductivity strengthens.Electro-conductive glass is slotted and line current extraction element substantially as described before is installed.Thus, line passes battery hermetically in the side of this battery, and is knitted together and/or pass through such as to be welded to connect to electric current collection band (not shown), to form the anode terminal of battery 300.Conductive bond oxidant layer 312 is applied in each groove 308, this layer is preferably chemical inertness to cell electrolyte and plays wire 316 is connected to the effect in groove 308, makes have good bridging electrical contact on each of groove 308 with stannic oxide layer (conductive surface layer 304) simultaneously.As an embodiment, titanium, tungsten or high-quality alloy wire can be inserted in groove 308, and the conductive adhesive preferably including the conductor such as titanium nitride and the binding agent such as aluminium oxide can also add in groove 308.
In structure battery 300, before applying nano-crystalline titanium dioxide layer, the upper surface of conductive bond oxidant layer 312 can be covered with insulating barrier 324, to prevent from being short-circuited between anode and negative electrode.When the surface of conductive bond oxidant layer 312 is far above sintering nano-crystalline titanium dioxide layer 320 (as shown in Figure 3 a), this is even more important.
Insulating barrier 324 is selected from glaze or the adhesive composition of the most coarse titanium dioxide, zirconium oxide, aluminium oxide or silica dioxide granule containing the characteristic particle size with several microns, or selectively, selected from high temperature polymer such as polyimides or siloxanes.At tin oxide surface (conductive surface layer 304) upper applying nano-crystalline titanium dioxide layer, this is typically by screen printing sizing agent, is subsequently dried and sinters to generate sintering nano-crystalline titanium dioxide layer 320.This sinter layer is designed to the typical thickness after a sintering step with about 15 microns.Based on electric insulation and/or the purpose of light back scattering, titanium dioxide layer 320 is optionally coated with coarse particles layer (not shown) based on titanium dioxide, zirconium oxide, aluminium oxide or silicon dioxide.In the construction process of battery 300, can cover titanium dioxide layer 320 with sensitiser dye subsequently, this step can be carried out subsequently, before filling electrolyte.With non-corrosive metal (NCM) sheet 368 closing battery, this sheet metal has used the catalyst Conventional catalytic of such as Trace Amounts of Platinum crystallite 332, and has used the sealant 336 of electrolyte-resistant to be sealed to anode glass 300 in each edge by this.Copper that titanium, titanium be coated with, tungsten can be included as the suitable constructions material of sheet metal 368 or mainly include the high-quality alloy of siderochrome or siderochrome molybdenum.
Importantly, by using the binding agent 340 of one layer of electrolyte-resistant, sheet metal 368 is bonded to the electrically insulating material of the rising of insulating barrier 324.Suitably binding agent is available, such as based on siloxanes or polyimides.Adhesive phase 340 can be spaced apart to maintain firm anchoring and uniform spacing between sheet 368 and anode glass 302 with periodic spacing along the material covering groove 308.Laterally continuous adhesive phase is operable to, but, but it is probably disadvantageous, because it is with the electrolyte being hydraulically isolated between adjacent grooves, and it is the most laborious to make electrolyte fill battery 300.
Fig. 3 b shows the setting of the anchor point in the schematic plan of battery 300, the most each "+" mark 303 represents the spaced position of the groove being placed with binding agent on positive plate.
Sheet 368 in Fig. 3 a can be slotted in a complementary fashion in anode glass 302, to accept the profile of the rising of insulating barrier 324 with such as requiring, between the surface of the surface of catalyst 332 and titanium dioxide layer 320, thus realize desired close proximity (only tens microns).Battery can be filled electrolyte via the hole (not shown) of sheet metal 368, seals hole subsequently.
According to desired separation criteria, the various selectable embodiment building double plate design is all possible.In fig. 3 a, positive plate can be mounted with the line of conductive metal band rather than embedding.Similarly, sheet metal based on auxiliary electrode can be the pattern as groove by punch forming simply.In one preferred embodiment, auxiliary electrode can be the flat sheet metal of mild catalytic, from sheet metal punching or cut out slit so that slit is mounted on the ascending member on groove, make the catalytic surface between slit reach close proximity with following titanium dioxide surface simultaneously.In this case, being placed on the glass on the plate of band slit or polymer sheet will be for closing battery, and at the multiple points that will be anchored on ascending member of this glass or polymer.
Fig. 4 provides the schematic cross section of double plate photovoltaic dye cells 400 according to another implementation of the invention.The configuration of this pair of plate battery can only use single electro-conductive glass sheet by each battery.This configuration realizes the juxtaposition closely of anode and negative electrode further.The photo cathode support glass or the substrate 402 that are coated with the conductor layer 404 of substantial transparent can have spaced, the most parallel line 410, this line passes through the most inert conductive adhesive layer correct position that such as conductivity ceramics adhesive phase 415 is bonded on the surface of electro-conductive glass (such as, on the top of conductor layer 404).It it is the nanocrystalline porous titanium dioxide layer of sintering 406 that usually 10-15 micron is thick between the edge of chemically inert current collection line 410 and battery 400.Owing to line 410 can typically have the diameter of at least 100 microns, and the height of titanium dioxide layer 406 is typically below about 15 microns, so line 410 can protrude past 80 microns on titanium dioxide layer 406.Short circuit in order to avoid the auxiliary electrode 430 of battery 400, it can be advantageous to electric insulation layer 418, such as, include that zirconic layer covers layer of ceramic adhesive 415.Electric insulation layer 418 can typically have the thickness in 20-50 micrometer range.
Battery 400 can have two physically separated electrodes.Thus, negative electrode or auxiliary electrode 430 can be in the different parts on anode component, and can be configured to close proximity anode component.Auxiliary electrode 430 can advantageously comprise porous, electrically conductive cathode layer 425, as supported the porous support matrix of impregnated carbon.Porous matrix can include or is substantially made up of pad, weaven goods and/or non-woven fabric, foam or other possible matrixes known in the art.Preferred material for pad is glass fibre, because its low cost, flexibility and may conform to cell geometry, in chemical inertness in battery context, it is possible to withstand high solidification or sintering temperature.Other fibers such as carbon fiber can also be used.By inert binder, impregnated carbon can be bonded to porous support matrix, inert binder can selected from as aluminium oxide inorganic material or as politef (PTFE or) polymeric material.
Auxiliary electrode 430 can include that porous cathode layer 425 and Catalytic Layer 432(Catalytic Layer 432 are arranged towards titanium dioxide layer 406) or a combination thereof.Porous cathode layer 425 can be arranged in battery 400 with many bands, and the width that every band has can make between the adjacent protrusions that band is arranged on layer 418, or adjacent cells periphery, between the projection of layer 418 and the inwall of (interior) edge seal 465.
Can affect from negative electrode or the current draw of auxiliary electrode 430 via the graphite foil 435 on the band (and being commonly angled relative to band physical separation) being placed in porous cathode layer 425.In its periphery, graphite foil 435 can have inert metal net at least partially embedded, that may highlight outside battery 400 or paper tinsel 440 to promote cathode current collector.
Dye cell 400 can be manufactured according to following Promethean method: there is transparent conductor layer 404(such as the transparent Indium tin layers of conduction) photo cathode support glass 402 surface on be the screen printing brush of titania slurry.Once sinter, generate the spaced apart band of sintered porous titanium dioxide layer 406.Current collection line 410 is positioned in each gap of adjacent titanium dioxide interband.Chemically inert conductivity ceramics slurry can be printed around line 410.Can be at the printed on top electric insulation slurry of ceramic material.Sintering operation makes layer of ceramic adhesive 415 chemical bonding to transparent conductor layer 404.Sintering makes electric insulation layer 418 chemical bonding to layer of ceramic adhesive 415.
In this, titanium dioxide band may be stained by dyestuff.
The auxiliary electrode of battery 400 includes the band of the porous conductive layer 425 being placed on the band of titanium dioxide layer 406.These bands can advantageously comprise the fiberglass packing that impregnated of the conductive carbon pastes experiencing sintering.The band of conductive layer 425 can use Catalytic Layer 432 to be advantageously catalyzed, and this Catalytic Layer 432 may be included in the Trace Amounts of Platinum catalyst on its surface.These bands can be placed directly within the sintered titanium dioxide layer 406 of photo cathode, and wherein Catalytic Layer 432 is arranged towards titanium dioxide layer 406.Although this direct contact, but it have been found that in the band of impregnated carbon, it is unnecessary for making carbon isolate further with titanium dioxide.
It is advantageously accomplished current draw via the graphite foil 435 on the band being placed in conductive layer 425.Graphite foil 435 has inert metal net or the paper tinsel 440 of the embedding that can pass this battery hermetically in its periphery.Carry out sealed cell 400 by glass pane lid 445 together with internal edge sealing member 465 and external margin sealing member 470, preferably produced by the polymer that two kinds of orders apply.Glass cover 445 applies enough pressure with the good electrical contact of the element that guarantees in battery and close spacing to following graphite foil.Electrolyte is added in battery and can be carried out by the filling hole (not shown) on glass pane, and its mesopore is subsequently by polymeric seal.Extracting cathode current via the extraction terminal 442 outside the wall of battery 400 from this battery, described terminal is formed by by the wire netting of cell wall or the sealable projection of paper tinsel 440, as by edge seal 465 and 470.Electric current collection band (not shown) can will can be soldered to form photo cathode current collector from the single line of the salable appearance of photo cathode via edge seal 465 and 470.
In solar energy module, single battery can be electrically connected or install aptly on the support structure.
Being apparent from according to foregoing, negative electrode 430 forms discrete, physically separated layer relative to the porous silica titanium film 406 of anode.Negative electrode 430 is also applied for showing compressibility and elastic value.Form a sharp contrast (wherein in order to prevent from damaging with negative electrode substantially free of productivity in prior art; negative electrode must keep certain distance with the surface of the crisp porous silica titanium film of anode); the band of negative electrode 430(and especially conductive layer 425) can be retained as leaning on the surface of porous silica titanium film 406, and absorbable normal modest pressure for porous silica titanium film 406 is to protect titanium dioxide film 406.Additionally, the bottom surface of negative electrode 430 can be suitable for or meet the profile of titanium dioxide film 406 so that significantly reduce the serious ohm poor efficiency characterizing various dye cells of the prior art.
In order to make band reach the degree of consistency of necessity, the band of conductive layer 425 can have the Shore D hardness less than 90.In some cases, the band of conductive layer 425 can have less than 80, or the Shore D hardness less than 70.
In the schematic cross section of the photovoltaic dye cell according to another preferred embodiment of the present invention as shown in Figure 5, substantially can build anode part as Fig. 3 a.Auxiliary electrode plate or lid include glass pane 578, by peripheral seal 556, as used fluid sealant, in edge, this glass pane is bonded to anode glass 302.For electric insulation and the purpose of light back scattering, can be with the nano-crystalline titanium dioxide layer 320 of coarse particles layer 322 coated anode based on titanium dioxide, zirconium oxide, aluminium oxide or silicon dioxide.Before electrolyte is filled, sensitiser dye coated with nano crystal titanium dioxide layer 320 can be used subsequently, or this step can be carried out subsequently.On the cathode plane of battery 500, as each groove at least one groove of groove 588 contains the wire 596 being bonded on correct position by conductive adhesive layer 592, wherein this adhesive phase also serves as pantostrat and extends and spread all over glass surface to provide conductivity in adjacent grooves.By layer of adhesive 566, anode and contrary plate can be bonded together at different points (as periodic intervals is interval) along anode with anti-groove (countergroove) (from the most the same).Between adjacent grooves, it is provided that the layer 570 of carbon or graphite, it is optionally coated with catalyst, such as Trace Amounts of Platinum, and selects the thickness of this layer to allow carbon or catalyst surface and nano-crystalline titanium dioxide layer 320 close proximity.Battery 500 can fill electrolyte by the filling hole (not shown) in auxiliary electrode, seals this hole subsequently, and at this moment, battery 500 can be prepared to test and modularity.There is the anchor point (e.g., being separated by about 1cm in the area battery of a size of 15cm × 15cm) closely placed and use strong binding agent such as siloxanes maintain spacing in battery 500 and prevent short circuit.
Although describing the present invention already in connection with specific embodiment, but many replacement scheme, modifications and variations being obvious to one skilled in the art.Therefore, it is desirable to comprise all such replacement schemes, modifications and variations.The all publications and patents mentioned in this description at this by be incorporated to identical degree with as each single publication or patent clearly and individually and carry out quoting herein by quoting and be incorporated by description.Additionally, the quoting or confirm to be not construed as recognizing that such reference is available as the prior art of the present invention of the most any reference.
Claims (18)
1. with the ohmic loss reduced, light source being changed into an electric photovoltaic dye cell, a single photovoltaic dye cell of described battery includes:
A () room, described room is applicable to surround described photovoltaic cell, and described room includes at least partly transparent cell wall with inner surface；
B () electrolyte, described electrolyte is placed in described cell wall, and described electrolyte contains redox materials；
C conductive coating that () is at least partly transparent, described conductive coating is arranged on the described inner surface of described at least partly transparent cell wall in described photovoltaic cell；
(d) anode, described anode is arranged on described conductive coating, and described anode includes:
I () porous silica titanium film, it is applicable to be in close contact with described redox materials；And
(ii) dyestuff, it is absorbed on the surface of described porous silica titanium film, and described dyestuff is applicable to converting photons is become electronics with described porous silica titanium film；
(e) negative electrode, described negative electrode is oppositely arranged with described anode, and described negative electrode includes at least one flexible conduction carbon plate being applicable to transfer an electron to the current collectingmembers relevant to described negative electrode,
(f) at least one metal tape or line, it is relevant to described anode and described conductive coating electricity,
Described conduction carbon plate is configured to communicate with the electrolysis of described porous silica titanium film via described electrolyte,
Described conduction carbon plate forms discrete layer relative to the described porous silica titanium film of described anode,
Wherein, the conduction carbon plate of described flexibility is suitable to consistent with the profile of described porous silica titanium film,
Wherein, the length and width of described single battery all at least 5 centimetres,
Wherein said discrete layer refers to and contact adjacent layers but the most different layers.
2. with the ohmic loss reduced, light source being changed into electric photovoltaic dye cell as claimed in claim 1, wherein said at least one metal tape or line have enough thickness with the projection being formed in the plane of described porous silica titanium film prominent at least 50 microns.
3. with the ohmic loss reduced, light source being changed into electric photovoltaic dye cell as claimed in claim 2, described at least one metal tape or line are many lines, and described projection is multiple projections.
4. with the ohmic loss reduced, light source being changed into electric photovoltaic dye cell as claimed in claim 3, described conduction carbon plate forms multiple self-supporting bar, and described self-supporting bar is arranged between described projection.
5. with the ohmic loss reduced, light source being changed into electric photovoltaic dye cell as claimed in claim 4, described self-supporting bar is arranged between described projection so that the surface of described conduction carbon plate is parallel with the described surface of described porous silica titanium film.
6. light source is changed into electric photovoltaic dye cell by the ohmic loss with reduction as according to any one of claim 1-5, and described conduction carbon plate is supported by flexible porous support matrix, and the porous support matrix of described flexibility includes fiber mat.
7. light source is changed into electric photovoltaic dye cell by the ohmic loss with reduction as according to any one of claim 1-5, and wherein said current collectingmembers contains by weight less than 2%, less than 1%, or the binding agent less than 0.5%, or binder free.
8. the photovoltaic dye cell that with the ohmic loss reduced light source changed into electricity as according to any one of claim 1-5, wherein said conduction carbon plate includes that the glass fiber tape of impregnated carbon, the glass fiber tape of wherein said impregnated carbon directly contact with the described surface of described porous silica titanium film.
9. light source is changed into electric photovoltaic dye cell by the ohmic loss with reduction as according to any one of claim 1-5, and the surface of described negative electrode is less than 7 microns with the surface distance of described porous silica titanium film.
10. light source is changed into electric photovoltaic dye cell by the ohmic loss with reduction as according to any one of claim 1-5, and the lid of wherein said single battery is suitable to apply pressure to described current collectingmembers and be suitable to promote the close space length of element in described photovoltaic dye cell.
Light source is changed into electric photovoltaic dye cell by 11. ohmic losses with reduction as any one of claim 1-5, and described current collectingmembers includes graphite foil.
Light source is changed into electric photovoltaic dye cell by the ohmic loss with reduction of 12. such as claim 4 or 5, and wherein said current collectingmembers includes graphite foil, and described graphite foil is relative to described self-supporting bar physical discrete.
Light source is changed into the photovoltaic dye cell of electricity by 13. ohmic losses to reduce as claimed in claim 11, also including the metallic conductive element being connected with described graphite foil, described metallic conductive element extends through the sidewall of described photovoltaic dye cell to affect current draw.
Light source is changed into electric photovoltaic dye cell with the ohmic loss reduced by 14. as claimed in claim 13, and wherein said metallic conductive element is metal forming or wire netting.
The 15. photovoltaic dye cells that with the ohmic loss reduced light source changed into electricity as according to any one of claim 1-5, the length and width of wherein said single battery all at least 10 centimetres.
Light source is changed into electric photovoltaic dye cell with the ohmic loss reduced by 16. as claimed in claim 9, and the surface of wherein said negative electrode is less than 3 microns with the surface distance of described porous silica titanium film.
Light source is changed into electric photovoltaic dye cell with the ohmic loss reduced by 17. as claimed in claim 9, and the surface of wherein said negative electrode directly contacts with the surface of described porous silica titanium film.
Light source is changed into electric photovoltaic dye cell by 18. ohmic losses with reduction as according to any one of claim 1-5, and wherein said conduction carbon plate is supported by flexible porous support matrix, and the porous support matrix of described flexibility includes glass fibre.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US96831607P | 2007-08-28 | 2007-08-28 | |
| US60/968,316 | 2007-08-28 | ||
| ILPCT/IL2008/000671 | 2008-05-15 | ||
| PCT/IL2008/000671 WO2008139479A2 (en) | 2007-05-15 | 2008-05-15 | Photovoltaic cell |
| PCT/IL2008/000856 WO2009001343A2 (en) | 2007-06-24 | 2008-06-24 | Dry cell having a sintered cathode layer |
| ILPCT/IL2008/000856 | 2008-06-24 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880113787.5A Division CN101842905B (en) | 2007-08-28 | 2008-08-28 | Photovoltaic dye cell having an improved counter-electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102969167A CN102969167A (en) | 2013-03-13 |
| CN102969167B true CN102969167B (en) | 2016-08-03 |
Family
ID=40387971
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210365063.8A Expired - Fee Related CN102969167B (en) | 2007-08-28 | 2008-08-28 | There is the photovoltaic dye cell of the auxiliary electrode of improvement |
| CN200880113787.5A Expired - Fee Related CN101842905B (en) | 2007-08-28 | 2008-08-28 | Photovoltaic dye cell having an improved counter-electrode |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880113787.5A Expired - Fee Related CN101842905B (en) | 2007-08-28 | 2008-08-28 | Photovoltaic dye cell having an improved counter-electrode |
Country Status (2)
| Country | Link |
|---|---|
| CN (2) | CN102969167B (en) |
| WO (1) | WO2009027977A2 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2533352A4 (en) * | 2010-02-03 | 2015-04-22 | Nippon Steel & Sumikin Chem Co | Dye-sensitized solar cell and method for manufacturing the same |
| US9129751B2 (en) * | 2010-03-29 | 2015-09-08 | Northern Illinois University | Highly efficient dye-sensitized solar cells using microtextured electron collecting anode and nanoporous and interdigitated hole collecting cathode and method for making same |
| KR101152544B1 (en) * | 2010-07-29 | 2012-06-01 | 삼성에스디아이 주식회사 | Electrode for photoelectric conversion device, method of preparing the same and photoelectric conversion device comprising the same |
| KR101132032B1 (en) * | 2010-08-11 | 2012-04-02 | 삼성에스디아이 주식회사 | Electrode for photoelectric conversion device, method of preparing the same and photoelectric conversion device comprising the same |
| CN102155078B (en) * | 2010-12-28 | 2012-07-04 | 德州学院 | Nanometer solar fabric photovoltaic surface skin |
| US9257601B2 (en) | 2011-05-17 | 2016-02-09 | Mcmaster University | Light emitting diodes and substrates |
| EP2642570B1 (en) * | 2012-03-23 | 2015-12-16 | Institute of Nuclear Energy Research Atomic Energy Council, Executive Yuan | A current collection apparatus and method of processing for a solid oxide fuel cell thereof |
| CN104584163A (en) * | 2012-08-22 | 2015-04-29 | 住友大阪水泥股份有限公司 | Dye-sensitive solar cell paste, porous light-reflective insulation layer, and dye-sensitive solar cell |
| US9405164B2 (en) | 2013-08-21 | 2016-08-02 | Board Of Trustees Of Northern Illinois University | Electrochromic device having three-dimensional electrode |
| CN104485230A (en) * | 2014-12-18 | 2015-04-01 | 中国科学院上海硅酸盐研究所 | Novel counter electrode for dye-sensitized solar cell and preparation method thereof |
| FR3082356B1 (en) * | 2018-06-11 | 2020-06-19 | Armor | PROCESS FOR MANUFACTURING A PHOTOVOLTAIC MODULE AND PHOTOVOLTAIC MODULE THUS OBTAINED |
| PL3896709T3 (en) * | 2020-04-17 | 2023-09-25 | Exeger Operations Ab | A photovoltaic device |
| CN115764003B (en) * | 2022-10-11 | 2023-07-21 | 贵州梅岭电源有限公司 | Zinc-silver accumulator used for multiple times under microgravity environment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1582501A (en) * | 2001-11-08 | 2005-02-16 | 查尔摩斯技术转让Ab | A photovoltaic element and production methods |
| CN1875433A (en) * | 2003-10-28 | 2006-12-06 | 住友金属矿山株式会社 | Transparent conductive multilayer body, method for manufacturing same and device using transparent conductive multilayer body |
| CN101017856A (en) * | 2007-03-06 | 2007-08-15 | 大连轻工业学院 | Dye sensitizing solar battery carbon pair electrode and preparing method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2003103085A1 (en) * | 2002-06-04 | 2005-10-06 | 新日本石油株式会社 | Photoelectric conversion element |
| IL153895A (en) * | 2003-01-12 | 2013-01-31 | Orion Solar Systems Ltd | Solar cell device |
| KR100661116B1 (en) * | 2004-11-22 | 2006-12-22 | 가부시키가이샤후지쿠라 | Electrode, photoelectric conversion element, and dye-sensitized solar cell |
| CN100355090C (en) * | 2005-04-21 | 2007-12-12 | 中山大学 | Stereo absorption filament integrated dye sensitization solar cell |
-
2008
- 2008-08-28 CN CN201210365063.8A patent/CN102969167B/en not_active Expired - Fee Related
- 2008-08-28 CN CN200880113787.5A patent/CN101842905B/en not_active Expired - Fee Related
- 2008-08-28 WO PCT/IL2008/001168 patent/WO2009027977A2/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1582501A (en) * | 2001-11-08 | 2005-02-16 | 查尔摩斯技术转让Ab | A photovoltaic element and production methods |
| CN1875433A (en) * | 2003-10-28 | 2006-12-06 | 住友金属矿山株式会社 | Transparent conductive multilayer body, method for manufacturing same and device using transparent conductive multilayer body |
| CN101017856A (en) * | 2007-03-06 | 2007-08-15 | 大连轻工业学院 | Dye sensitizing solar battery carbon pair electrode and preparing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101842905A (en) | 2010-09-22 |
| CN102969167A (en) | 2013-03-13 |
| WO2009027977A3 (en) | 2009-04-30 |
| CN101842905B (en) | 2013-01-16 |
| WO2009027977A2 (en) | 2009-03-05 |
| WO2009027977A4 (en) | 2009-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102969167B (en) | There is the photovoltaic dye cell of the auxiliary electrode of improvement | |
| US9704653B2 (en) | Photovoltaic cell | |
| US9530572B2 (en) | Solar cell device | |
| AU2007231352B2 (en) | A sealed monolithic photo-electrochemical system and a method for manufacturing a sealed monolithic photo-electrochemical system | |
| US8586861B2 (en) | Solar cell device | |
| AU2019269021B2 (en) | A photovoltaic device | |
| AU2017230039B2 (en) | A solar cell comprising grains of a doped semiconducting material and a method for manufacturing the solar cell | |
| AU2009250946B2 (en) | Photovoltaic cell | |
| JP4954855B2 (en) | Manufacturing method of dye-sensitized solar cell | |
| JP5441916B2 (en) | Large area dye battery and production method thereof | |
| EP3627527A1 (en) | Photovoltaic device for powering an external device and a method for producing the photovoltaic device | |
| WO1998034251A1 (en) | Photovoltaic cell | |
| WO2009053979A2 (en) | Monolithic dye cell assembly having reduced ion migration in intercell seals |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160803 Termination date: 20190828 |