EP1828838A1 - Flexible electrochemical cell with controlled optical absorption and reflection having an aqueous electrolyte - Google Patents
Flexible electrochemical cell with controlled optical absorption and reflection having an aqueous electrolyteInfo
- Publication number
- EP1828838A1 EP1828838A1 EP05825617A EP05825617A EP1828838A1 EP 1828838 A1 EP1828838 A1 EP 1828838A1 EP 05825617 A EP05825617 A EP 05825617A EP 05825617 A EP05825617 A EP 05825617A EP 1828838 A1 EP1828838 A1 EP 1828838A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hfp
- pvdf
- peo
- electrochemical cell
- mixture
- 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.)
- Withdrawn
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 12
- 238000010521 absorption reaction Methods 0.000 title abstract description 5
- 230000003287 optical effect Effects 0.000 title description 6
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 150000002500 ions Chemical class 0.000 claims abstract description 25
- 238000003780 insertion Methods 0.000 claims abstract description 17
- 230000037431 insertion Effects 0.000 claims abstract description 17
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- 239000004020 conductor Substances 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 230000000295 complement effect Effects 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010494 dissociation reaction Methods 0.000 abstract description 2
- 230000005593 dissociations Effects 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract description 2
- 239000011229 interlayer Substances 0.000 abstract 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 30
- 238000010586 diagram Methods 0.000 description 10
- 239000011149 active material Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- -1 Na + Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- CXKGGJDGRUUNKU-UHFFFAOYSA-N oxotungsten;hydrate Chemical compound O.[W]=O CXKGGJDGRUUNKU-UHFFFAOYSA-N 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
- G02F1/15165—Polymers
Definitions
- the invention relates to a flexible electrochemical cell, aqueous, controlled emission.
- United States Patent No. 0 296 318 discloses a 5 rechargeable battery comprising
- This battery uses different powders which are incorporated into a polymer matrix in the form of a film. This structure provides two advantages. First, this
- films formed from the various components of a battery can be laminated together with grid current collectors to form a fully flexible cell.
- the cells developed by this technique of the prior art utilize a hydrophobic copolymer polymer of vinylidene fluoride and hexafluoropropylene (PVDF-HFP). They therefore use organic solvents such as
- Dimethylcarbonate, propylene carbonate, ethylene carbonate or acetonitrile are not controlled emission cells. They use an organic medium that does not favor the rapid insertion of ions.
- the electrochemical cell according to the invention has a particular arrangement of the layers which compose it in order to be able to observe the optical properties providing ion access to the electroactive material.
- the subject of the invention is therefore an electrochemical cell in thin layers having a variable emissivity as a function of an applied control voltage, characterized in that it is formed of the following flexible elements superimposed and respectively in intimate contact:
- a first current collector made of electrically conductive material and intended to be connected to a first potential of the control voltage
- porous counterelectrode formed of a mixture of PVDF-HFP, PEO, optionally at least one other hydrophilic polymer, and a powder of an insertion ion reservoir compound or capable of absorbing ions complementary to the insertion ions,
- porous separator formed of a mixture of PVDF-HFP and PEO
- a second current collector of electrically conductive material intended to be connected to a second potential of the control voltage and capable of being traversed by ions; a porous electronic conduction layer formed of a mixture of PVDF-HFP; PEO and a powder of an electrically conductive material,
- porous active layer formed of a mixture of PVDF - HFP, PEO and a powder of an insertion material, the counter electrode, the separator, the electronic conduction layer and the active layer being filled with an aqueous electrolyte.
- the first and second current collectors may be grids. These grids may be metallic (aluminum, copper or lead for example) and preferably stainless, ITO. They may be stainless steel advantageously covered with a mixture of carbon and the PVDF-HFP copolymer.
- the mixture of PVDF-HFP and PEO in the flexible elements comprises, by weight, between 80% and 50% of PVDF-HFP and between 20% and 50% of PEO.
- the ion reservoir compound comprising ions complementary to the insertion ions may be selected from H x WO 3 , H x WO 3 - H 2 O, H x MoO 3 , a polymer such as polyaniline (PANI) or carbon activated, preferably coated with polymer.
- PANI polyaniline
- the insertion ions are ions such as Na + , Mg 2+ that can be inserted into materials such as WO 3 - H 2 O and WO 3 .
- the electrically conductive material of the electronic conduction layer may be selected from graphite carbon and metals.
- the aqueous electrolyte may in particular contain sulfuric acid.
- FIG. 1 is a diagram showing caking curves for various polymer mixtures used to produce the electrochemical cell according to the invention
- FIG. 2 is a diagram representing the electrical conductivity as a function of the concentration of sulfuric acid for copolymers used to produce the electrochemical cell according to the invention
- FIG. 3 represents a diagram of the arrangement of different composite films for constituting an electrochemical cell according to the invention
- FIG. 4 is a diagram showing the evolution of the current and the load during cycling
- FIG. 5 is a diagram illustrating the optical properties of the electrochemical cell according to the invention.
- the PVDF-HFP copolymer is hydrophobic.
- this copolymer is very interesting because of these remarkable mechanical properties.
- PEO Polyethylene oxide
- FIG. 1 is a diagram showing% PM caking curves for different PVDF-HFP and PEO mixtures as a function of the absorption time t in minutes.
- the PVDF-HFP copolymer used comprises 12 mol% of HFP.
- Curve 1 corresponds to the PVDF-HFP copolymer (hence without PEO).
- Curve 2 corresponds to a mixture comprising 80% by weight of PVDF-HFP and 20% by weight of PEO.
- Curve 3 corresponds to a mixture comprising 60% by weight of PVDF-HFP and 40% by weight of PEO.
- Curve 4 corresponds to a mixture comprising 50% by weight of PVDF-HFP and 50% by weight of PEO.
- the bell shape of the curves shows that the PEO dissolves in the water. It is the PVDF-HFP which ensures the mechanical strength. Compositions greater than 50% by weight of PEO have been tested. They do not have sufficient mechanical strength. However, the addition of a silica filler should allow the percentage of PEO to be further increased.
- PVDF-HFP (comprising 12 mol% of HFP), 2 g of di-n-butyl phthalate (DBP) which serves as plasticizer and acetone are added.
- DBP di-n-butyl phthalate
- the solution is then mixed for 15 minutes at an approximate speed of 2000 rpm before being spread on a glass plate using a scraper to control the thickness of the deposit. After evaporation of the solvents, films in the form of ribbons 5 cm wide and about 1.2 m long are obtained.
- Figure 2 is a diagram showing the electrical conductivity for different concentrations of H 2 SO 4 and different concentrations by weight of PEO in the mixture of PVDF-HFP and PEO.
- Curve 5 was plotted for a concentration of H 2 SO 4 equal to 1 M.
- Curve 6 was plotted for a concentration of H 2 SO 4 worth 0.1 M.
- Plastic films in a mixture of PVDF-HFP and PEO having active materials can be made in the same way, but by adding at the end of manufacture the active materials in powder form. An active material / polymer ratio of 3.66 (weight ratio) was used. It is also possible to use a larger quantity of active material.
- Figure 3 is a schematic diagram of the arrangement of different composite active material-polymer films to obtain an electro-active device operating in visible light and infrared.
- the cell of FIG. 3 comprises in superposition a collector 11, a counter-electrode 12, a separator 13, a collector 14, a graphite-based film 15 and an active material film 16.
- the films 11 to 16 are assembled from way to achieve an "optical battery”.
- the current collectors 11 and 14 are stainless steel grids (mesh size of the grids approximately 0.5 mm). To make these grids less sensitive to the electrolyte, they can be covered with a mixture of carbon and PVDF-HFP (comprising 12 mol% of HFP). This hydrophobic mixture makes it possible to improve the behavior of the collectors during cycling.
- the counter-electrode may comprise an acid-stable insertion material or activated carbon.
- Counter-electrode 12 may consist of H x WO 3 -H 2 O (with 0 ⁇ x ⁇ 0.35) in a mixture comprising 60% by weight of PVDF-HFP (at 12 mol% of HFP) and 40% by weight of PEO.
- the separator 13 consists of a mixture comprising 50% by weight of PVDF-HFP (12 mol% of HFP) and 50% by weight of PEO.
- the film comprises carbon (between 30 and 60% by weight) in a mixture comprising 50% by weight of PVDF-HFP (12 mol% of HFP) and 50% by weight of PEO.
- This film makes it possible to ensure a better distribution of the electrical charges on the film of active material 16.
- the film of the active material 16 comprises WO3 tungsten oxide monohydrate. H2O in a mixture of 60% by weight of PVDF-HFP (12 mol% of HFP) and 40% by weight of PEO.
- the material WO 3 - H 2 O may be replaced by any species which is stable in acidic medium and capable of interposing protons.
- the thickness of the active layer 16 may be 9 ⁇ m.
- the thickness of the separator 13 may be between 10 ⁇ m and 100 ⁇ m.
- FIG. 4 shows different curves for the electrochemical cell described above and at 50 mV / s.
- This value of 50 mV / s represents the cycling speed of the cell, that is to say the speed of the evolution of the potential set by the user.
- the ordinate axis on the left represents intensity I.
- the ordinate axis on the right represents the x coefficient of the compound H x WO 3 - H 2 O in the counter electrode 12.
- the abscissa represents the potential of the Ewe working electrode in volts.
- Figure 4 shows that there is insertion of ions and thus that the system operates from an electrochemical point of view.
- FIG. 5 is a diagram illustrating the optical properties of the electrochemical cell according to the invention.
- This diagram represents the reflection (in%) of the cell as a function of the wavelength ⁇ .
- Curve 21 corresponds to the reservoir compound of ions H x WO 3 - H 2 O.
- Curve 22 corresponds to the reservoir compound WO 3 ions. H 2 O.
- the curve 22 corresponds to the active layer 16 before insertion (WO 3 - H 2 O) and the curve 21 corresponds to the active layer 16 after insertion (H x WO 3 - H 2 O).
- This figure shows that the cell has a modulation of the reflection in the infrared.
- This figure also shows the absence of absorption band in the infrared due to the use of water as a solvent.
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Separators (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0453111A FR2879764B1 (en) | 2004-12-21 | 2004-12-21 | ELECTROCHEMICAL CELL FLEXIBLE, AQUEOUS, WITH CONTROLLED EMISSION |
PCT/FR2005/051106 WO2006067354A1 (en) | 2004-12-21 | 2005-12-19 | Flexible electrochemical cell with controlled optical absorption and reflection having an aqueous electrolyte |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1828838A1 true EP1828838A1 (en) | 2007-09-05 |
Family
ID=34953628
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05825617A Withdrawn EP1828838A1 (en) | 2004-12-21 | 2005-12-19 | Flexible electrochemical cell with controlled optical absorption and reflection having an aqueous electrolyte |
Country Status (7)
Country | Link |
---|---|
US (1) | US7722986B2 (en) |
EP (1) | EP1828838A1 (en) |
JP (1) | JP2008524822A (en) |
CN (1) | CN101128772B (en) |
FR (1) | FR2879764B1 (en) |
SG (1) | SG158161A1 (en) |
WO (1) | WO2006067354A1 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2969323B1 (en) | 2010-12-15 | 2013-08-16 | Commissariat Energie Atomique | ALL-SOLID ELECTROCHROME DEVICE, TWO-LAID ELECTRODE FOR THIS DEVICE, AND METHOD FOR THE PREPARATION THEREOF |
ES2637799T3 (en) | 2011-11-15 | 2017-10-17 | Ashwin-Ushas Corporation, Inc. | Electrochromic device with complementary polymers |
CN104037388B (en) * | 2013-03-07 | 2016-09-14 | 纳米及先进材料研发院有限公司 | Transparent or semitransparent lithium ion battery and electrode thereof |
US9207515B2 (en) | 2013-03-15 | 2015-12-08 | Ashwin-Ushas Corporation, Inc. | Variable-emittance electrochromic devices and methods of preparing the same |
EP2972573B1 (en) * | 2013-03-15 | 2019-06-19 | Ashwin-Ushas Corporation, Inc. | Variable-emittance electrochromic devices and methods of preparing the same |
US10483595B2 (en) * | 2013-10-16 | 2019-11-19 | Suzhou Hans Energy Storage Technology Co., Ltd. | Tungsten-based material super battery and supercapacitor |
US8902486B1 (en) | 2013-11-20 | 2014-12-02 | Ashwin-Ushas Corporation, Inc. | Method and apparatus for control of electrochromic devices |
CN103713439B (en) * | 2013-11-30 | 2017-01-04 | 西安科技大学 | The flexible stealthy device of a kind of adjustable infrared emittance and assemble method thereof |
GB201411985D0 (en) * | 2014-07-04 | 2014-08-20 | Enocell Ltd | Battery |
JP2018518798A (en) * | 2015-06-30 | 2018-07-12 | ▲張▼雨虹 | Doped conductive oxide and improved electrode for electrochemical energy storage devices based on this material |
US9632059B2 (en) | 2015-09-03 | 2017-04-25 | Ashwin-Ushas Corporation, Inc. | Potentiostat/galvanostat with digital interface |
US9482880B1 (en) | 2015-09-15 | 2016-11-01 | Ashwin-Ushas Corporation, Inc. | Electrochromic eyewear |
CN113156729B (en) * | 2020-01-07 | 2022-07-08 | 苏州苏大维格科技集团股份有限公司 | Flexible electrochromic device and manufacturing method thereof |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5296318A (en) * | 1993-03-05 | 1994-03-22 | Bell Communications Research, Inc. | Rechargeable lithium intercalation battery with hybrid polymeric electrolyte |
US5587872A (en) * | 1995-10-25 | 1996-12-24 | Motorola, Inc. | Electrochemical cell having symmetric inorganic electrodes |
JP4829453B2 (en) * | 1999-09-30 | 2011-12-07 | エバレデイ バツテリ カンパニー インコーポレーテツド | Electrochemical cell having ultra-thin separator and method for producing the same |
FR2841045B1 (en) * | 2002-06-17 | 2004-12-24 | Electricite De France | LITHIUM ACCUMULATOR |
-
2004
- 2004-12-21 FR FR0453111A patent/FR2879764B1/en not_active Expired - Fee Related
-
2005
- 2005-12-19 US US11/793,105 patent/US7722986B2/en not_active Expired - Fee Related
- 2005-12-19 EP EP05825617A patent/EP1828838A1/en not_active Withdrawn
- 2005-12-19 WO PCT/FR2005/051106 patent/WO2006067354A1/en active Application Filing
- 2005-12-19 SG SG200908522-6A patent/SG158161A1/en unknown
- 2005-12-19 CN CN2005800438763A patent/CN101128772B/en not_active Expired - Fee Related
- 2005-12-19 JP JP2007547593A patent/JP2008524822A/en active Pending
Non-Patent Citations (1)
Title |
---|
See references of WO2006067354A1 * |
Also Published As
Publication number | Publication date |
---|---|
CN101128772A (en) | 2008-02-20 |
US20080131773A1 (en) | 2008-06-05 |
SG158161A1 (en) | 2010-01-29 |
WO2006067354A8 (en) | 2007-10-04 |
FR2879764A1 (en) | 2006-06-23 |
US7722986B2 (en) | 2010-05-25 |
FR2879764B1 (en) | 2007-03-23 |
WO2006067354A1 (en) | 2006-06-29 |
JP2008524822A (en) | 2008-07-10 |
CN101128772B (en) | 2013-03-27 |
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