• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to an electrode for an electrochemical cell which is a piece of monocrystal grown from doped titanium dioxide or which contains a plurality of monocrystals (2) grown from doped titanium dioxide.
    公开号:AT511433A4
    申请号:T1628/2011
    申请日:2011-11-03
    公开日:2012-12-15
    发明作者:Wolfgang Dipl Ing Mag Wesner；Michael Dr Schelch；Wolfgang Dr Staber；Robert Ing Mag Hermann
    申请人:Pro Aqua Diamantelektroden Gmbh & Co Kg；
    IPC主号:
    专利说明:

    C3.Ncv.2C11 17:21 ΟC43130351C520 DIPL ING EDITH VINAZZER # 2931 P.0C4 / 016 1 per aqua diamond electrodes production GmbH & Co KG PA 8277 s electrode, its use and an electrochemical cell
    The invention relates to an electrode for an electrochemical cell, its use 10 and an electrochemical cell.
    In electrochemical cells usually electrodes are used with a mixed oxide coating, which have as Tragennetall especially titanium or niobium on which precious metal oxides of the plating droplet with other valve metals, such as aluminum, tantalum, niobium, manganese, titanium, bismuth, antimony, zinc, cadmium, Zirconium, tungsten, tin, iron, silver and silicon. For chloride-free electrolytes usually iridium mixed oxide coatings are used, for the production of chlorine and hypochlorite ruthenium or iridium / ruthenium mixed oxide coatings. It is also known to use platinized titanium or niobium anodes for certain applications, such as hard chrome plating, precious metal coating or metal recovery. Such anodes are made of a titanium or niobium carrier in the form of expanded metal, in Stabfoim, in wire form, in tube form or the like, on which platinum or noble metal oxides are applied in layer thicknesses up to 20 μκι in several operations. The life of these anodes depends in particular on the working medium, the electrolyte, and the anodic current and is limited by the gradual removal of the applied layer and by the change in polarity during operation.
    It is also known to use in electrochemical cells diamond electrodes of doped diamond particles which are embedded in a non-conductive support layer. Such diamond electrodes are characterized by a high overvoltage for 03/11/2011 15:44
    No .: R938 P 004/016 03.Kov.2011 17:21 00431503510520 DIPL ING EDITH VINAZZER # 2931 P.005 / 016 Ci · k I * * • · * »2
    Oxygen and hydrogen and are therefore particularly suitable for a variety of oxidation processes in aqueous solution. A diamond electrode made of synthetically produced, electrically conductive, boron-doped diamond particles is known, for example, from WO 2004/005585 A1. In this diamond electrode, the diamond particles 5 are superficially embedded in a metal or metal alloy layer. From WO 2007/116014 A2 a diamond electrode is known in which the doped diamond particles are embedded in a non-conductive carrier layer and are exposed on both sides of the carrier layer. A plastic-based diamond electrode for electrochemical applications is known from WO 2006/116298 A1. This electrode has, at least on its surface, a layer of synthetically produced doped diamond particles. The basically non-conductive Kunststoffgrundköipcr can be made electrically conductive by admixing conductive components.
    Such diamond electrodes have been well proven in practice, since they are pronounced I s resistant and longer life than the metallic described above
    Have electrodes.
    The invention has for its object to provide an electrode which has a longer life than the previously known electrodes. 20
    The object is achieved according to the invention in that the electrode is a piece of a crystal grown from doped titanium dioxide or contains a plurality of crystals grown from doped titanium dioxide. From doped titanium dioxide in crystal form, it is possible to produce or provide electrodes which have a markedly long service life, which by far exceeds the service life of the known electrodes.
    It is of particular advantage that the crystal piece can be a crystal plate cut from the grown crystal 30. Such electrodes can be in different 03/11/2011 15:45
    N °: R938 P.005 / 016 .Ncv.2011 17:21 00431503510520 DIPL ING EDITH VINAZZER # 2931 P.00 6/016
    * · * · 3
    Shapes, sizes and thicknesses, in particular in a thickness of 0.5 mm to 10 mm. preferably up to 3 mm, cut from the cultivated crystal.
    In an electrode of a plurality of crystals, these are embedded in a single layer in a carrier layer of a non-conductive material, wherein the crystals are exposed on both sides of the carrier layer. Also in this design a long life is guaranteed.
    Polytetrafluoroethylene 10 (Teflon), polyvinylidene fluoride (PVDF), perfluoroalkoxyalkane (PFA), fluorinated material are used in particular as material for the carrier layer (1)
    Ethylene propylene (FEP), ethylene tetrafluoroethylene (ETFE), polyether ether ketone (PEEK), polyphenylene sulfide (PPS), polyethylene (PE), polypropylene (PP) or polyvinyl chloride (PVC). According to the invention, the crystals embedded in the support layer have a particle size between 100 μm and 5 mm, in particular between 200 μm and 800 μm, and are grown in this size. The grain size is adapted to the thickness of the carrier layer. According to the invention, one of the elements lithium, niobium, aluminum, phosphorus, gallium, bur, arsenic, indium, germanium, iridium, ruthenium, rhodium, antimony, nitrogen, manganese, iron, cobalt, nickel, chromium or titanium is used for doping the titanium dioxide Yttrium or their oxides or fluorides used. Owing to their long service life, electrodes according to the invention are suitable above all for use as edge electrodes in an electrochemical cell both as an anode and as a cathode.
    Also advantageous is the use of an electrode according to the invention as a bipolar electrode in an electrochemical cell. 03/11/2011 15:45
    No .: R938 P.006 / 016 C3.Nov.Z0Ii 17:22 00431503SIC5ZO DIPL INC EDITH VINAZZER # 2531 P.007 / 016 • · · 4
    The invention further relates to an electrochemical cell which contains as an edge electrode (s) an electrode or electrodes, which is or are designed according to the invention. The electrochemical cell may further include at least one diamond electrode as a bipolar electrode. 5
    In an alternative embodiment of an electrochemical cell, this contains as bipolar electrode (s) one or more electrodes, which are electrodes designed according to the invention. 10 Further features, advantages and details of the invention will become apparent from the following description and will be described with reference to the schematic drawing illustrating exemplary embodiments. Show
    FIG. 1 is a sectional view of a portion of an electrode according to the invention; and FIG
    Fig. 2 is a sectional view during the manufacture of the electrode.
    The invention is concerned with the manufacture and implementation of an electrode anode or cathode for an electrochemical cell. The electrode should have a much higher lifetime than the previously known electrodes with mixed oxide coating.
    In one embodiment of the invention, the electrode consists of a particular plate-shaped piece of a monocrystal grown from doped titanium dioxide (TiCh). To produce such electrodes, correspondingly large crystals are grown, which in the desired shape, for example rectangular or round, and with the desired
    Thickness, in particular between 0.5 mm and 10mm, preferably up to 3 mm, cut. The doping takes place in the starting material or during the crystal growth in the melt. For the necessary to achieve the electrical conductivity doping is a variety of elements in question, for example, lithium, niobium, aluminum, phosphorus 30, gallium, boron, arsenic, indium, germanium, iridium, ruthenium, rhodium, antimony, nitrogen, manganese, iron , Cobalt, nickel, chromium or yttrium or the oxides 03/11/2011 15:46
    No .: R938 P.007 / 016, Ν ον, 2 011 17:22 00431503510520 DIPL IMS EDITH VINAZ2EP. # 2531 P.OCB / 016 5 or fluorides of said elements. There are thus those elements b2w. their oxides / fluorine in question, which are trivalent or pentavalent. Particularly suitable are iridium and ruthenium. For the growth of the titanium dioxide crystals, the methods known for the growth of single crystals are suitable, in particular the methods for crystal growth from a melt, such as the method of Bridgman-Stockbarger. This method allows the growth of single crystals at a qualitatively and quantitatively high level. In another embodiment of the invention, the electrode consists of a
    Support material embedded in a nonconductive plastic small single crystal grown from doped titanium dioxide 2.
    Fig. 1 shows an embodiment of such an electrode, wherein the crystals 2 15 are embedded in one layer and without mutual contact with each other in a plastic carrier layer 1 and projecting on both sides of the carrier layer 1 slightly and are ffeigelegt.
    The crystals 2 may have particle sizes between about 100 gm to a few millimeters, 20 especially up to 5 mm. Preference is given to particle sizes between 200 | xm and 800 .mu.m ». For a particular electrode crystals 2 are used with substantially identical grain size, wherein the thickness of the support layer 1 is adapted to the grain size. The crystals 2 are doped with one of the above-mentioned doping elements, their oxides or fluorides, and therefore are electrically conductive. The crystals 2 are grown in the desired particle size according to known methods as monocrystals.
    The starting material for the backing layer 1 are in a preferred embodiment, films of chemically stable polymers, in particular polytetrafluoroethylene (Teflon), 30 Pölyvinylidenflourid (PVDF), perfluoroalkoxylalkane (PFA), fluorinated ethylene propylene (FEP), ethylene-tetrafluoroethylene (ETFE), polyetheretherketone (PEEK ), Polyethylene (PE), 03/11/2011 15:46
    No .: R938 P.008 / 016 03.Hov.2CIi 17:23 C043i503SiOS2G DIPL IKG EDITH VIHA2ZER # 2531 P.CCS / C16
    6
    Polypropylene (PP), polyvinyl chloride (PVC) or polyphenylene sulfide (PPS). To produce the carrier layer 1, two films 4, 5 or film webs of the same material are used in a starch which is matched to the crystal sizes. On a horizontally or substantially horizontally and just positioned film 4, a layer 5 of crystals 2 is applied. Subsequently, the second film 5 on the with the
    Crystals 2 provided first sheet 4 and the two sheets 4, 5 are connected to each other between the crystals 2. The two sheets 4, 5 is preferably carried out by applying pressure on both sides by, for example, the film composite in a press or between two rollers Pressure is exercised. If the films are also heated, they melt and combine with each other. If the crystals 2 are already exposed on both sides as a result of the applied pressure on both sides, no aftertreatment is necessary. However, it is possible to subsequently expose the crystals 2 in a mechanical, chemical or thermal manner. In order to avoid a subsequent exposure of the crystals 2, it is advantageous if all the crystals 2 are already exposed on joining the two films 4, 5 on the outer sides of the film. In a preferred embodiment, therefore, the first film 4 is placed on a thin plate 3 of a soft, resilient material and placed on the outside of the second film 5 already positioned also a thin plate 20 of this material, as shown in Figure 2 , Now, pressure can be exerted on one or both sides and heat can be supplied so that the foils 4, 5 are melted and joined together. The crystals 2 penetrate through the film material and are exposed. As a preferred material for these thin, yieldable plates 3 are for example Teflon 25 (polytetrafluoroethylene), Viton and Kapton (fluoroelastomers of DuPont Finn), neoprene (chloroprene Kauschuk (or polychloroprene or chlorobutadiene rubber), thermoplastic vulcanizates (TPV), Fluororubbers, for example, copolymers of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) and terpolymers of VDF, HFP and tetrafluoroethylene (TFE), further fluorinated elastomers such as, for example, perfluoro rubber 30 (FFKM), tetrafluoroethylene / propylene rubbers (FEPM) and fluorinated silicone rubber (VQM), as well as silicones, but also metals such as lead, aluminum or 03/11/2011 15:46
    No .: R938 P.009 / 016, Νον.ΣΪΠ 17:23 00431503511520 DIPL ING EDITH VINAZZER # 2531 P.01C / 016 Φ * · · • * * 7
    Copper. The thickness of the plates 3 is chosen between 0.2 mm to 3 mm, in particular between 0.5 mm and 1.5 mm. If necessary, can subsequently be carried out in a further processing step exposure of crystals 2 in a mechanical, chemical or thermal manner. 5
    To increase the mechanical strength of the finished electrode, in the production of the electrode on or below the film 4 and / or on the applied crystals 2 one or more layers a Sttitzgitter, support fabric 6 or the like can be positioned. Subsequently, as described, the connection of the two film webs to 1 ö production of the carrier layer 1 and to expose the crystals 2. Alternatively, it is possible, the support grid, supporting fabric 6 or the like after completion of the electrode on an outer side or on both outer sides of To attach electrode, for example by sticking or lamination. Suitable materials for the grid or support fabric 6 are plastics such as polytetrafluoroethylene (Teflon), 15 Polyvinylidenflourid (PVDF), Pcrfiuoralkoxylalkan (PFA), fluorinated ethylene propylene (FEP), ethylene-tetrafluoroethylene (ETFE), polyetheretherketone (PEEK) or polyphenylene sulfide (PPS ), Glass fibers, plastic-coated glass fibers, ceramics or metals. Electrodes designed or manufactured according to the invention are particularly suitable for use in electrolysis cells (electrochemical cells), in particular for drinking water treatment, for the disinfection of drinking water, for water treatment by anodic oxidation, for the production of oxidizing agents and for the electrolysis of water and electrochemical Production of ozone and chlorine. A preferred use is in electrochemical cells for purifying water in swimming pools, whirlpools or hot tubs.
    From a crystal stucco existing electrodes are particularly suitable as edge electrodes, embedded in a support layer crystals on facing electrodes as bipolar electrodes 30. On a Randelektrodc can one-sided an electrically conductive 03/11/2011 15:47
    No .: R938 P.010 / 016
    03.Kov.2CU 17:23 OC431503S10 & 2C
    3IP1 ING EDITH VINA22ER # 2931 P.CU / 016 I · f 8
    Contacting layer can be attached, which makes it possible to provide the crystal optimally and permanently with electricity.
    It is also possible to combine electrodes according to the invention with electrodes of the prior art in an electrochemical cell, for example to use diamond electrodes as edge electrodes or as bipolar electrodes. 03/11/2011 15:47
    No .: R938 P.011 / 016 03.Kov.20i: 17:24 C043150351052C DIPL ING EDITH VINAZZER # 2931 P.012 / 016 I * * * 9 • - * * * * * 5 Reference numbers lfl 1 .... ................ backing layer 2 ....................... crystal 3 ....... ................ Plate 4 ....................... Slide 5 ....... ................ Foli 15 6 ....................... Support grid 03/11/2011 15: 47
    No .: R938 P. 012/016
    权利要求:
    Claims (14)
    [1]
    1. Electrode for an electrochemical cell, characterized in that it is a piece of a grown from doped titanium dioxide 03.Nov.2011 17:24 00431503510520 DIPL ING EDITH VINAZZER # 2S31 P.013 / 016 Single crystal or contains a plurality of monocrystals (2) grown from doped titanium dioxide.
    [2]
    2, electrode according to claim 1, characterized in that the crystal piece is a cut from the grown crystal crystal plate.
    [3]
    3. An electrode according to claim 2, characterized in that the thickness of the crystal plate between 0.5 mm and 10 mm, in particular up to 3 mm.
    [4]
    4. An electrode according to claim 1, characterized in that the plurality of 20 crystals is embedded in a single layer in a carrier layer (1) made of a non-conductive material, wherein the crystals (2) on both sides of the carrier layer (1) are exposed.
    [5]
    5. An electrode according to claim 1 or 4, characterized in that the crystals (2) 25 have a particle size between 100 pm and 5 mm, in particular between 200 and 800 pm, wherein the grain size is adapted to the thickness of the carrier layer (1) ,
    [6]
    6. Electrode according to one of claims 1 to 5, characterized in that the 30 titanium dioxide with lithium, niobium, aluminum, phosphorus, gallium, Bur, arsenic, indium, germanium, iridium, ruthenium, rhodium, antimony, nitrogen, manganese, 03 / 11/2011 15:48 No .: R938 P, 013/016 03.Kov.20i: η: 24 0C4 31 31032C DIPL ING EDITH VLMAZZER # 2931 C14 'Ci 6 Π iron, cobalt, nickel, chromium or yttrium or with the oxides or fluorides of said elements is doped.
    [7]
    7. An electrode according to claim 4 or 5, characterized in that the carrier layer 5 (1) of polytetrafluoroethylene (Teflon), Polyvinyüdenflourid (PVDF), perfluoroalkoxylalkane (PFA), fluorinated ethylene propylene (FEP), ethylene-tetrafluoroethylene (ETFE), PoJyetheretherketon ( PEEK), polyphenylene sulfide (PPS), polyethylene (PE), polypropylene (PP) or polyvinyl chloride (PVC).
    [8]
    8. Use of the electrode according to one of claims 1 to 3 or 6 as an edge electrode in an electrochemical cell.
    [9]
    9. Use of the electrode according to claim 8 as an anode.
    [10]
    10. Use of the electrode according to claim 8 as Kaihode.
    [11]
    11. Use of the electrode according to one of claims 1 or 4 to 7 as a bipolar electrode in an electrochemical cell.
    [12]
    12. An electrochemical cell which contains as an edge electrode (s) an electrode or electrodes, which is or are executed according to one or more of claims 1 to 3 or 6.
    [13]
    13. An electrochemical cell according to claim 13, which contains at least one diamond electrode as a bipolar electrode.
    [14]
    14. An electrochemical cell which contains as a bipolar electrode (s) an electrode or electrodes which is or are executed according to one or more of claims 1 or 4 to 7. 03/11/2011 15:48 No .: R938 P.014 / 016
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    US4003817A|1967-12-14|1977-01-18|Diamond Shamrock Technologies, S.A.|Valve metal electrode with valve metal oxide semi-conductive coating having a chlorine discharge in said coating|
    US4144147A|1977-09-26|1979-03-13|E. I. Du Pont De Nemours And Company|Photolysis of water using rhodate semiconductive electrodes|
    US5364508A|1992-11-12|1994-11-15|Oleh Weres|Electrochemical method and device for generating hydroxyl free radicals and oxidizing chemical substances dissolved in water|
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    法律状态:
    2013-11-15| HC| Change of the firm name or firm address|Owner name: PRO AQUA DIAMANTELEKTRODEN PRODUKTION GMBH & C, AT Effective date: 20131008 |
    2020-08-15| MM01| Lapse because of not paying annual fees|Effective date: 20191103 |
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