EP3380651A1 - Metal hollow fiber electrode - Google Patents
Metal hollow fiber electrodeInfo
- Publication number
- EP3380651A1 EP3380651A1 EP16820029.3A EP16820029A EP3380651A1 EP 3380651 A1 EP3380651 A1 EP 3380651A1 EP 16820029 A EP16820029 A EP 16820029A EP 3380651 A1 EP3380651 A1 EP 3380651A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hollow fiber
- fibers
- fiber electrode
- metal hollow
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
Definitions
- the invention is directed to a metal hollow fiber electrode, to a method of electrolyzing carbon dioxide in an aqueous electrochemical cell, to a method of converting carbon dioxide, to a method of preparing a metal hollow fiber, to a use of a metal hollow fiber electrode.
- Copper electrodes are well known for producing hydrocarbons from CO2 with variable onset potentials ( ⁇ 0.5-0.7 V) depending on the preparation method. Generally, high potentials ( ⁇ 0.8-1 V) are necessary to obtain reasonable faradaic efficiency (FE). Although less expensive and much more abundant than other CO evolving catalysts such as e.g. silver and gold, poor activity, selectivity and stability towards CO and formic acid have been reported for polycrystalline copper. Recently, Li et al. reported production of CO and formic acid with reasonable faradaic efficiency at low overpotentials on copper nanoparticles, when formed by electrochemical reduction of cuprous oxides [Li et al., J. Am. Chem. Soc. 2012, 134, 7231- 7234].
- Inorganic hollow fibers are of potential significance for solid oxide fuel cells due to their high surface area to volume ratio, higher power outputs and lower fabrication costs, but utilization in room temperature solution based electrochemistry is quite rare.
- nickel and carbon hollow fibers with dual functionality, where they served as both membrane for effluent purification and as cathode for proton and oxygen reductions, respectively.
- microtubular gas diffusion electrodes made of carbon nanotubes were proposed for tubular
- An objective of the invention is to overcome one or more disadvantages seen in the prior art.
- a further objective of the invention is to provide an electrode that allows low pressure and room temperature electrolysis of CO2.
- the invention is directed to a metal hollow fiber electrode, comprising aggregated cooper particles forming an interconnected three-dimensional porous structure, wherein said metal comprises copper.
- metal hollow fiber electrodes can be a potential candidate for low pressure and room temperature electrolysis of CO2, due to their excellent mass transport capabilities when used as gas diffuser and cathode. Not only the hydrogen evolution reaction is suppressed on these electrodes to levels not reached previously on copper surfaces, but also the overall CO2 reduction current density is unprecedented ⁇ / high at low potentials.
- the metal comprises copper and other metals may optionally be present. More preferably, the metal is copper.
- the metal hollow fibers can typically have an inner diameter of
- the outer diameter of the metal hollow fibers can be 0.1-10 mm, such as 0.5-5 mm, or 0.7-3 mm.
- the fibers preferably comprise, or are composed of, sintered copper particles.
- Solid state sintering is the process of taking metal in the form of a powder and placing it into a mold or die. Once compacted into the mold the material is placed under a high heat for a long period of time.
- the copper particles in the metal hollow fiber electrode preferably have an average particle diameter of 0.1-10 ⁇ , such as 0.3-5 ⁇ , or 0.5-3
- a porous outer layer of the hollow fiber is more dense than a porous inner layer of the hollow fiber, said outer layer preferably having a thickness in the range of 5-20 ⁇ , such as 12-18 ⁇ , or 10-15 ⁇ .
- the preparation of the metal hollow fibers i.e. nickel and stainless steel has been described in the literature previously [Meng et al., J. Alloy Compd. 2009, 470, 461-464; Luiten-Olieman et al, Scripta Mater. 2011, 65, 25-28].
- the preparation of Cu hollow fiber has not been reported to the best of our knowledge. The inventors adapted the method and prepared Cu hollow fibers by spinning a mixture containing copper particles, polymer and solvent.
- the mixture is suitably pressed through a spinneret into a coagulation bath. In this bath, non-solvent induced phase separation arrests the copper particles in the polymer matrix.
- a hollow fiber is obtained.
- the polymer is decomposed and the copper particles are sintered together, resulting in hollow, porous copper oxide fibers. Hydrogenation of these precursor fibers at elevated temperatures was applied to obtain metallic copper fibers.
- Typical scanning electron microscope (SEM) images of the Cu hollow fibers are shown in figure 1. The low and higher
- magnification images of the external surface of the fibers show that the fiber is composed of aggregated copper particles forming an interconnected 3-D porous structure (figure la and lb).
- the cross-sectional images of the deliberately broken fibers exhibit fingerlike voids perpendicular to the surface which are terminated by a 10-15 ⁇ thick sponge-like porous outer layer (figures lc and Id).
- Cu hollow fibers can have outer and inner diameters ranging from 1.55 ⁇ 0.1 mm to 1.3 ⁇ 0.05 mm respectively (figure le). CO2 was pushed from the inside out of the fiber, creating an
- the first step involves an electron transfer to adsorbed CO2 which is coupled to a proton transfer.
- COOH intermediate accepts an electron and proton to form CO and water.
- a slope around 116 mVdec 1 was recorded for copper different electrodes that suggests a mechanism in which initial electron transfer to CO2 is rate determining.
- the lower slope of 93 mVdec" 1 associated with the lower potential region is most likely due to non-uniform potential or current distribution within the solid porous matrix of the hollow fiber. This might be either caused by the ohmic drop within solid porous matrix or
- Figures 3a and 3b show the effect of the CO2 flow rate on overall current density and faradaic efficiency of CO at an applied voltage of -0.4 V vs. RHE, respectively.
- the current density undoubtedly is proportional to the CO2 flow rate above -0.35 V vs. RHE, until a certain flow rate was reached.
- the change in faradaic efficiency of CO is consistent with the increase in current density.
- a maximum faradaic efficiency of 75 % was recorded for CO at a potential of -0.4 V vs. RHE at optimized flow rate which is almost twice of what has been recently reported for copper nanoparticles at the same potential.
- the experiments as a function of flow rate indicate that the faradaic efficiency of CO strictly depends on supply of CO2 to the electrode surface.
- Cu hollow fibers can reduce CO2 to CO electrochemically at a potential of -0.4 V vs. RHE, with over 15 to 400 times higher rate than polycrystalline Cu and Cu nanop articles, respectively at a potential of -0.4 V vs. RHE.
- Cu hollow fibers While outcompeting the currently best performing copper based electrodes, Cu hollow fibers also show comparable activities at low potentials (-0.2 V to -0.6 V vs. RHE) to that of noble metal catalysts evaluated in aqueous solutions (Au nanoparticles, nanoporous Ag). It should be recalled that noble metal electrodes benefit from a high overpotential for hydrogen evolution, while Cu hollow fibers perform so well on the basis of the improved mass transfer of CO2.
- the thickness of the porous catalyst layer used in gas diffusion electrodes is typically in the range from 5-20 ⁇ , similarly for copper hollow fibers, the electrode thickness that participates into the electrolysis is around 15-20 ⁇ estimated from nickel electrodeposition and subsequent energy dispersive X-ray analysis (figure 10). This thickness is also comparable to oxide films used to prepare rough electrodes or electrodeposited 3-D porous structures employed as electrodes.
- the geometrical current density of the fibers are calculated by normalizing the current to the outer surface area of the cylindrical hollow fibers. In addition, it is a common practice to use the projected area of the 3-D electrode, or so called apparent area, in conventional gas diffusion electrodes to report current densities.
- the mature dry-wet spinning process allows mass production of organic hollow fibers that are already commercially available.
- Microtubular geometry has been deployed and investigated in solid oxide fuel cells for decades which could allow the adaptation of technologies developed such as stack design, sealing, current collection etc.
- Metal hollow fibers might provide cost effective and compact diffusion media and/or catalyst layer for gas diffusion electrodes which might also eliminate resistance associated with catalyst support interface. Furthermore, we believe there is plenty of room to increase the production rate by considering the controllability of the internal and external structure of the hollow fibers.
- the thickness of the active catalyst layer can be tuned by changing 3-D geometry, support material, porosity and/or precursor particle size, to further optimize the production rate.
- the invention is directed to a method of electrolyzing carbon dioxide in an aqueous electrochemical cell comprising an anode and a cathode, wherein the cathode comprises one or more metal hollow fiber electrodes according to the invention, said method comprising
- the method of the invention is performed in an aqueous environment.
- the invention is directed to a method of converting carbon dioxide into one or more selected from the group consisting of carbon monoxide, formic acid, a formate, methanol,
- the carbon dioxide is converted into carbon monoxide.
- the invention is directed to a method of preparing a metal hollow fiber electrode according to the invention, comprising:
- the thermal treatment in this method preferably comprises subjecting the hollow fibers to a temperature in the range of 500-800 °C, such as in the range of 550-700 °C. This thermal treatment is preferably performed for a period of 1-6 hours, such as a period of 2-5 hours.
- hydrogenation comprises subjecting the hollow copper oxide fibers to a flow of hydrogen in the concentration range of 0.1-100 vol.%, such as 5 vol.% in a balance gas.
- the invention is directed to the use of a metal hollow fiber electrode according to the invention as cathode and/or gas diffuser.
- NMP N-methylpyrrolidone
- PEI Polyetherimide
- the fibers were kept in the coagulation bath for 1 day to remove traces of NMP, followed by drying for 1 day.
- the green copper hollow fibers were thermally treated at 600 °C for 3 hours (heating rate and cooling rates: 1 °C min -1 ) in air to remove the PEI and subsequent sintering of the copper particles.
- the oxidized hollow fibers were reduced by hydrogenation at 280 °C for 1 hour (3 ⁇ 4 in Argon: 4 %, heating rate and cooling rate: 100 °C/min).
- X-ray diffraction patterns were collected by using a Bruker D2 Phaser x-ray diffractometer, equipped with a Cu- ⁇ radiation source and operated at 30 kV and 10 mA (figure 5).
- X-ray photoelectron spectroscopy (XPS) spectrum was collected by using Quantera SXM (Scanning XPS microprobe) spectrometer equipped with Al Ka (1486.6 eV) X-ray source. The source was operated with a 25 W emission power, beam size of 200 ⁇ and pass energy of 224 eV. The resolution of the spectrometer was O. leV and 0.2 eV for high resolution element scan and survey spectra, respectively.
- AH solutions were prepared and all glassware were cleaned by using deionized water (Millipore MilliQ, 18.2 ⁇ ). Electrochemical CO2 reduction activity of Cu HF's was measured by using three electrode assembly in a glass cell at room temperature and pressures. A Princeton Applied Research versaSTAT 3 potentiostat was used to control the potentials. The counter electrode, Pt mesh, was separated by using a Nafion 112 membrane (Sigma Aldrich). An Ag/AgCl (3 M NaCl BASI) reference electrode was placed near the working electrode by using a Luggin capillary and all the potentials were converted to RHE scale afterwards. IR drops were measured before the electrolysis and compensated manually after the experiments.
- thermal conductivity detector TCD
- flame ionization detector FID
- TCD thermal conductivity detector
- FID flame ionization detector
- EDX Energy dispersive X-ray analysis
- X-ray photoelectron spectroscopy was collected by using
- Quantera SXM (Scanning XPS microprobe) spectrometer equipped with Al Ka (1486.6 eV) X-ray source.
- the source was operated with a 25 W emission power, beam size of 200 ⁇ and pass energy of 224 eV.
- the resolution of the spectrometer was 0.1 eV and 0.2 eV for high resolution element scan and survey spectra, respectively.
- High resolution elemental scans are performed for Cu, C, O, Al, Ni, Fe, Pb, Cd, Hg.
- the minimal detectable amount changes with the sensitivity factors for the elements. As a rule of thumb: lighter elements have smaller sensitivity factors and are less good
- Table 3 The atomic concentrations of the elements calculated from the intensities of the peaks present in XPS spectra
- Figure 1 Physical characterization of Cu hollow fibers, a) Low and b) High magnification SEM images of the outer surface of the Cu hollow fiber, c) Cross-sectional image of perpendicularly broken Cu hollow fiber, d) Outer surface of parallel broken Cu hollow fiber along with the cross-section, e) Image of Cu hollow fiber taken by the electron microscope, and f) Cu hollow fiber employed as an electrode (20 ml min- 1 gas flow and no applied potential.
- Faradaic efficiency (FE) of CO, formic acid and 3 ⁇ 4 at different potentials c) Overpotential vs. partial current density of CO for Cu hollow fiber, d) Total production of CO at an applied potential of -0.4 V for 24 hours of continuous experiment (flow rate of CO 2 : 20 ml min 1 ).
- FIG. 3 Electrocatalytic performance as a function of flow rate, a) Linear polarization curves for different flow rates of CO2 (Scan rate 50 mV s" 1 ). b) Faradaic efficiency (FE) of CO for different flow rates of CO2 and corresponding current densities (applied potential of -0.4 V vs. RHE, 0.3 M KHCO3. * Experiments are performed in CO2 saturated solutions.
- Figure 4 Activity of various electrodes in water: Overview of different catalysts' performance at different potentials with a plot of partial current density of CO at different potentials.
- Figure 5 XRD patterns of the starting copper powder, Cu hollow fiber after calcination at 600 °C, and the copper fiber after hydrogenation..
- Figure 6 SEM image of "as received" copper powder.
- Figure 7 The faradaic efficiency (FE) of CO and total current density at an applied potential of -0.4 V for 24 hours of continuous experiment (flow rate of CO2: 20 ml min- 1 ).
- Figure 10 EDX analysis demonstrating the wt.% of electrodeposited nickel as a function of location from the outer surface. Deposition of Ni was achieved on the copper hollow fibers feeding 20 ml min- 1 of argon through the porous wall into the Ni 2+ solution.
- Figure 11 SEM image of Cu hollow fiber showing the locations of the SEM images taken to construct figure 1.
- Figure 12 X-ray photoelectron spectroscopy survey for copper hollow fibers before electrolysis (includes 5 repeated scans).
- Figure 14 High-resolution X-ray photoelectron spectrum of the Cu LMM region for Cu hollow fibers after electrolysis. Some Cu(I) might be present in the material.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201562259089P | 2015-11-24 | 2015-11-24 | |
PCT/NL2016/050826 WO2017091070A1 (en) | 2015-11-24 | 2016-11-24 | Metal hollow fiber electrode |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3380651A1 true EP3380651A1 (en) | 2018-10-03 |
EP3380651B1 EP3380651B1 (en) | 2020-07-29 |
Family
ID=57681708
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16820029.3A Active EP3380651B1 (en) | 2015-11-24 | 2016-11-24 | Metal hollow fiber electrode |
Country Status (3)
Country | Link |
---|---|
US (1) | US20190271089A1 (en) |
EP (1) | EP3380651B1 (en) |
WO (1) | WO2017091070A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6779849B2 (en) * | 2017-09-19 | 2020-11-04 | 株式会社東芝 | Carbon dioxide reduction catalyst and its production method, reduction electrode, and reduction reactor |
KR102140710B1 (en) * | 2018-06-22 | 2020-08-03 | 한국과학기술원 | High pressure reactor for carbon dioxide conversion and method for operating thereof |
CN114395777A (en) * | 2022-01-17 | 2022-04-26 | 中国科学院上海高等研究院 | Metal self-supporting electrode, preparation method and application |
CN114959761B (en) * | 2022-05-05 | 2023-11-03 | 中国科学院上海高等研究院 | Preparation method and application of silver hollow fiber electrode |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3035998A (en) * | 1957-05-08 | 1962-05-22 | Siemens Ag | Multi-purpose electrode for electrochemical processes |
US4329157A (en) * | 1978-05-16 | 1982-05-11 | Monsanto Company | Inorganic anisotropic hollow fibers |
US20150136613A1 (en) * | 2013-02-12 | 2015-05-21 | The Board Of Trustees Of The Leland Stanford Junior University | Catalysts for low temperature electrolytic co reduction |
WO2015051211A2 (en) * | 2013-10-03 | 2015-04-09 | Brown University | Electrochemical reduction of co2 at copper nanofoams |
-
2016
- 2016-11-24 WO PCT/NL2016/050826 patent/WO2017091070A1/en active Application Filing
- 2016-11-24 US US15/778,864 patent/US20190271089A1/en not_active Abandoned
- 2016-11-24 EP EP16820029.3A patent/EP3380651B1/en active Active
Also Published As
Publication number | Publication date |
---|---|
US20190271089A1 (en) | 2019-09-05 |
EP3380651B1 (en) | 2020-07-29 |
WO2017091070A1 (en) | 2017-06-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Liu et al. | CO 2 electoreduction reaction on heteroatom-doped carbon cathode materials | |
Han et al. | Defective graphene for electrocatalytic CO2 reduction | |
Kas et al. | Three-dimensional porous hollow fibre copper electrodes for efficient and high-rate electrochemical carbon dioxide reduction | |
Zhao et al. | Effective tunable syngas generation via CO2 reduction reaction by non-precious Fe-NC electrocatalyst | |
US9255335B2 (en) | Catalysts for low temperature electrolytic CO2 reduction | |
Sebastián et al. | CO2 reduction to alcohols in a polymer electrolyte membrane co-electrolysis cell operating at low potentials | |
Li et al. | Nitrogen-doped tubular carbon foam electrodes for efficient electroreduction of CO 2 to syngas with potential-independent CO/H 2 ratios | |
JP4907745B2 (en) | How to reduce carbon dioxide | |
JP5017499B2 (en) | How to reduce carbon dioxide | |
KR102411448B1 (en) | Oxygen-generating anode | |
EP3380651B1 (en) | Metal hollow fiber electrode | |
Wu et al. | Palladium decorated porous nickel having enhanced electrocatalytic performance for hydrazine oxidation | |
Chetty et al. | Direct ethanol fuel cells with catalysed metal mesh anodes | |
EP3543377A1 (en) | Apparatus for producing organic hydride and method for producing organic hydride | |
Sunitha et al. | Performance evaluation of nickel as anode catalyst for DMFC in acidic and alkaline medium | |
WO2014018091A1 (en) | Catalysts for low temperature electrolytic co2 or co reduction | |
WO2018037774A1 (en) | Cathode, electrolysis cell for producing organic hydride, and organic hydride production method | |
Wu et al. | Hierarchical and self-supporting honeycomb LaNi5 alloy on nickel foam for overall water splitting in alkaline media | |
Shi et al. | In situ reconstruction of vegetable sponge-like Bi 2 O 3 for efficient CO 2 electroreduction to formate | |
Yu et al. | JIN et al. | |
Shen et al. | Theoretical calculation guided design of single atom-alloyed bismuth catalysts for ampere-level CO2 electrolysis to formate | |
US7175751B2 (en) | Method and apparatus for electrorefining impure hydrogen | |
US8597488B2 (en) | Method for reducing carbon dioxide | |
Zhang et al. | Topological Conversion of Nickel Foams to Monolithic Single‐Atom Catalysts | |
WO2008096927A1 (en) | Method for generating hydrogen, apparatus for generating hydrogen, and electrically-driven system using the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20180611 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20190816 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20200408 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1295889 Country of ref document: AT Kind code of ref document: T Effective date: 20200815 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602016040988 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20200729 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1295889 Country of ref document: AT Kind code of ref document: T Effective date: 20200729 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201029 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201130 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201029 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201030 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201129 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602016040988 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602016040988 Country of ref document: DE |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
26N | No opposition filed |
Effective date: 20210430 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20201124 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201124 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20201130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201130 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201124 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210601 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201124 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201129 Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200729 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201130 |