EP1740739B1 - Cellule electrochimique - Google Patents

Cellule electrochimique Download PDF

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Publication number
EP1740739B1
EP1740739B1 EP05732004.6A EP05732004A EP1740739B1 EP 1740739 B1 EP1740739 B1 EP 1740739B1 EP 05732004 A EP05732004 A EP 05732004A EP 1740739 B1 EP1740739 B1 EP 1740739B1
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Prior art keywords
electrolyte
gap
gas
overflow
electrochemical cell
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EP05732004.6A
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German (de)
English (en)
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EP1740739A1 (fr
Inventor
Fritz Gestermann
Andreas Bulan
Hans-Dieter Pinter
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Covestro Deutschland AG
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Covestro Deutschland AG
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    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms

Definitions

  • the invention relates to an electrochemical cell, at least consisting of an anode half-cell with an anode, a cathode half-cell with a cathode and an ion exchange membrane arranged between anode half-cell and cathode half-cell, wherein the anode and / or the cathode is a gas diffusion electrode.
  • the invention further relates to a process for the electrolysis of an aqueous solution of alkali chloride.
  • WO 01/57290 An electrolytic cell with a gas diffusion electrode is known in which a porous layer is provided in the gap between the gas diffusion electrode and the ion exchange membrane. The electrolyte flows from top to bottom over the porous layer under the action of gravity through the gap.
  • the porous layer according to WO-A 01/57290 may consist of foams, wire nets or the like.
  • an electrolytic cell with gas diffusion electrode for the electrolysis of a sodium chloride solution in which a layer of a hydrophilic material is in the gap between the gas diffusion electrode and the ion exchange membrane.
  • the layer of hydrophilic material preferably has a porous structure containing a corrosion-resistant metal or resin.
  • a porous structure for example, nets, fabrics or foams can be used.
  • Sodium hydroxide, the electrolyte flows down the layer of hydrophilic material down to the bottom of the electrolytic cell under gravity.
  • EP-A 1 033 419 an electrolytic cell with gas diffusion electrode as a cathode for the electrolysis of a sodium chloride solution known.
  • a hydrophilic porous material through which the electrolyte flows.
  • porous material metals metal oxides or organic materials are considered, provided they are corrosion resistant.
  • Porous layers also have the disadvantage that gas which has once entered the porous structure, from this difficult to get out again.
  • the gas can accumulate, whereby the above-mentioned disadvantages arise.
  • Gas from the gas space can also pass from the gas space into the gap through the gas diffusion electrode under operating conditions.
  • gas diffusion electrodes tend to pass more gas at non-wetted sites, so that the effect amplifies.
  • the object of the present invention is therefore to provide an electrolytic cell which avoids the disadvantages of the prior art.
  • the invention relates to an electrochemical cell, at least consisting of an anode half-cell with an anode, a cathode half-cell with a cathode and an ion exchange membrane arranged between anode half-cell and cathode half-cell, wherein the anode and / or the cathode is a gas diffusion electrode, between the gas diffusion electrode and the ion exchange membrane Gap, an electrolyte inlet above the gap and an electrolyte drain below the gap and a gas inlet and a gas outlet is arranged, characterized in that the electrolyte inlet is connected to an electrolyte reservoir and has an overflow.
  • the electrolyte flows in the gap between gas diffusion electrode and ion exchange membrane from top to bottom through the half cell. Accordingly, in the electrolysis cell according to the invention there is an electrolyte feed above the gap and an electrolyte drain below the gap. The gap is completely filled by the flowing electrolyte.
  • the remaining space of the half-cell behind the gas diffusion electrode i. the space on the side facing away from the ion exchange membrane of the gas diffusion electrode, which is referred to as gas space, is filled with gas.
  • the gas is supplied to the gas space through the gas inlet and discharged through the gas outlet.
  • the Elektolytzulauf forms horizontally above the gap a channel which extends over the entire width of the electrochemical cell.
  • the electrolyte can be fed uniformly over the entire width from above into the gap between the gas diffusion electrode and the ion exchange membrane.
  • the electrolyte feed for example, has numerous openings which are directed downwards, over which the electrolyte flows during operation of the electrolytic cell into the gap.
  • a gap-shaped or slot-shaped opening may be provided, which extends over the entire width of the gap.
  • the electrolyte leaves the half-cell via the electrolyte drain and enters an electrolyte reservoir, wherein the electrolyte effluent must be immersed in the electrolyte reservoir to an uncontrolled gas flow through the electrolyte reservoir from cell to cell (in case of several electrolysis cells connected to an electrolyzer).
  • the electrochemical cell according to the invention is also referred to as a falling film cell.
  • Their trouble-free operation depends crucially on the safe supply of the electrode with electrolyte.
  • the width may be more than 2000 mm. This means that a uniform feeding of the electrode with electrolyte over the entire width must be guaranteed.
  • gas diffusion electrode is used as the electrode, gas can enter from the gas space through the gas diffusion electrode into the gap between the gas diffusion electrode and the ion exchange membrane. The gas must be able to be reliably removed from the gap, since an accumulation of gas in the gap must be avoided.
  • the uniform feeding of the gas diffusion electrode with electrolyte, which flows in the gap between gas diffusion electrode and ion exchange membrane from top to bottom, is achieved in the electrolysis cell according to the invention in that the electrolyte feed is connected to an electrolyte reservoir and has an overflow.
  • the electrolyte reservoir is preferably located 30 to 200 cm above the electrolyte inlet.
  • the electrolyte flows from the storage tank into the electrolyte inlet. From the electrolyte feed, the electrolyte flows e.g. via a slit-shaped opening in the gap between gas diffusion electrode and ion exchange membrane.
  • the electrolyte reservoir is connected via a pump to the electrolyte inlet.
  • the electrolyte reservoir can in principle be arranged at any desired location, for example below the electrochemical cell. With the help of the pump, the electrolyte is pumped with the desired form in the electrolyte inlet.
  • the electrolyte reservoir may, in principle, be connected at any location to the electrolyte inlet, e.g. at one end of the electrolyte inlet.
  • electrolysis cells according to the invention are connected to form an electrolyzer, a single electrolyte reservoir can be used to supply all the electrolysis cells of the electrolyzer.
  • each of the electrolysis cells can be equipped with a separate storage tank.
  • the electrolyte inlet according to the invention has an overflow.
  • the overflow preferably has a height of 0 to 190 cm, more preferably 1 to 190 cm above the entry into the gap. In principle, the height of the overflow can be less than 1 cm; The overflow is at the same level as the entry into the gap.
  • the overflow ensures that during operation of the electrolysis cell always accumulates a certain amount of electrolyte in the electrolyte feed. It is crucial for the height of the overflow to accumulate a large amount of electrolyte in the electrolyte feed sufficient to continuously supply electrolyte to the gap across its entire width.
  • a valve, a diaphragm, for example in the form of a perforated disc, or the like may be provided in the supply line, which connects the electrolyte reservoir with the electrolyte inlet.
  • a valve, a diaphragm for example in the form of a perforated disc, or the like may be provided in the supply line.
  • the targeted overflow of the electrolyte from the electrolyte inlet allows a uniform feeding of the gap with electrolyte over the entire width of the electrode and a safe discharge of gas from the gap.
  • the overflow stream prevents the level of electrolyte in the electrolyte feed from dropping enough for the falling film of the electrolyte in the gap to break off. Furthermore, the overflow ensures, inter alia, that gas bubbles which rise from the gap in the electrolyte feed are transported away with the electrolyte.
  • the overflow can in principle be positioned at any point along the electrolyte inlet. He can e.g. be provided at one end of the electrolyte inlet.
  • the overflow is designed according to the invention as an overflow channel.
  • Such an overflow channel can be arranged either outside or inside the cathode half cell. Excess electrolyte, which does not flow down the gap, flows from the electrolyte feed into the overflow channel and is removed from the overflow channel from the electrolytic cell, e.g. discharged into an electrolyte tank.
  • the overflow channel can be designed, for example, as a hose or pipe, possibly with a perforated cover or the like.
  • the overflow channel is e.g. directed upwards. This can e.g. be designed as a U-shaped channel, so that excess electrolyte first fills the connected to the electrolyte inlet leg of the U-shaped overflow channel and drains over the second leg again.
  • the overflow channel is directed upwards, e.g. U-shaped
  • the height between the upper vertex of the upflow channel and the electrolyte inlet (hereinafter referred to g) is preferably 0 to 190 cm, particularly preferably 1 to 190 cm. Likewise, this applies to any form of overflow.
  • the overflow channel can also be embodied as a standpipe or vertical shaft, channel or the like within the electrolysis half-cell.
  • the excess electrolyte is hereby removed from the electrolysis cell and passed, for example, into a collecting container.
  • the entry into the standpipe is preferably at least 1 cm above the Level of the gap to ensure uniform feeding across the full width of the cell.
  • the discharged via the overflow electrolyte is preferably passed into a collection container.
  • a collection container This may be achieved, for example, by a channel located outside the electrolytic cell, e.g. a hose or pipe done.
  • the collecting container may be connected to the storage container so that the electrolyte can be pumped from the collecting container into the storage container and re-supplied to the electrolytic cell.
  • the amount of electrolyte flowing from the receiver tank into the electrolyte feed depends on the height difference between the liquid level of the electrolyte in the feed tank and the liquid level in the electrolyte feed.
  • the height difference thus defined is also referred to below as h.
  • the liquid level in the electrolyte feed in turn, depends on the height of the overflow, which determines how much the electrolyte in the electrolyte feed is dammed up. If the electrolyte is supplied by means of a pump from the storage tank to the electrolyte feed, the amount of electrolyte which is conveyed into the electrolyte feed depends on the delivery head h of the pump.
  • an overflow channel may be provided which is arranged substantially horizontally. Excess electrolyte can also be removed from the electrolysis cell via such a horizontally arranged overflow channel.
  • the pressure in the electrolyte inlet can be set by selecting the height g of the overflow channel. As the pressure increases, more electrolyte can be passed through the gap. Thus, the gap can be acted upon at different current densities with different amounts of electrolyte. This is advantageous, for example, if the electrolyte is strongly concentrated at high current densities, which can cause damage to the ion exchange membrane. However, this can be avoided if the electrolyte is passed through the gap with a larger volume flow.
  • the pressure in the electrolyte inlet can be set in a targeted manner. It is important to note that g is less than or equal to h.
  • the advantage of the electrolysis cell according to the invention is that due to the simple principle of the free overflow a uniform feeding of the gap between the gas diffusion electrode and the ion exchange membrane and the safe removal of gas from the gap is possible.
  • the flow velocity in the gap can be easily regulated by means of the overflow.
  • a dangerous for the gas diffusion electrode dynamic pressure increase in the gap between gas diffusion electrode and membrane can be avoided, which could be caused for example by direct injection of the electrolyte by means of a pump without functioning free overflow of the electrolyte inlet.
  • Oxygen, air or oxygen-enriched air (hereinafter referred to simply as oxygen) is supplied from a template (also referred to as a gas collection container), preferably below the gas space, in the gas space of the half-cell with gas diffusion electrode.
  • the supply takes place via a gas distribution pipe as gas inlet uniformly over the entire width of the half-cell.
  • the unused oxygen is removed in the upper part of the half-cell via a gas outlet from the gas space.
  • the gas supply can also take place in the upper region and the gas removal in the lower region of the electrolysis half-cell.
  • the gas outlet is connected to the electrolyte reservoir, so that the electrolyte reservoir simultaneously serves as a gas reservoir for excess oxygen.
  • the unused oxygen is supplied from the gas space via a gas line as a gas outlet to the electrolyte reservoir, wherein the gas line preferably dips below the liquid level of the electrolyte. If the gas line immersed in the electrolyte reservoir and at the same time the electrolyte discharge is immersed in the electrolyte reservoir, the dipping of the gas line in the electrolyte reservoir must not be deeper than the immersion of the electrolyte discharge in the reservoir. The excess oxygen can be recycled for optimal utilization.
  • the electrolyte reservoir simultaneously serves as a gas collection container, has the advantage that only a storage container is required for the oxygen and the electrolyte.
  • the electrolyte reservoir can also be arranged below the electrolytic cell, wherein the electrolyte is conveyed from the electrolyte reservoir into the electrolyte inlet by means of a pump, provided that the free flow of the electrolyte excess is ensured via the overflow channel (control over not over-flowed overflow channel).
  • the gas outlet is connected to a gas collecting container and the gas space is closed relative to the gap.
  • the gas space can, for example by means of a Plate, such as a metal plate, be completed against the gap.
  • the gas collecting container is a separate collecting container, flows in the excess oxygen via a gas line as a gas outlet. In this way, the oxygen pressure can be adjusted independently of the pressure conditions in the gap.
  • the gas space has drainage openings at the lower end.
  • flow guide structures are provided in the gap.
  • the flow guide structures prevent a free fall of the electrolyte in the gap, so that the flow velocity is reduced compared to the free fall. At the same time, however, the electrolyte must not accumulate in the gap due to the Strömungsleit Weg.
  • the flow guide structures are selected so that the pressure loss of the hydrostatic liquid column in the gap is compensated. Examples of flow guiding structures are made WO 03/042430 and WO 01/57290 known.
  • the flow guiding structures may also consist of thin plates, foils or the like, which have openings for flowing through the electrolyte. They are transversal, i. perpendicular or oblique, arranged to the flow direction of the electrolyte in the gap.
  • the plate-shaped Strömungsleit Jardin are preferably inclined relative to the horizontal, wherein they are inclined either only in one axis or in both axes. If the flow guide structures are arranged obliquely to the flow direction, they can be inclined both in the direction of the ion exchange membrane and in the direction of the gas diffusion electrode. In addition, the flow guiding structures may be inclined across the width of the electrochemical cell.
  • Another object of the invention is a process for the electrolysis of an aqueous alkali halide solution in the electrochemical cell according to the invention.
  • the method is characterized in that the electrolyte from the electrolyte reservoir is supplied in excess to the electrolyte inlet, the electrolyte flows from the electrolyte inlet into the gap and out of the gap into the electrolyte outlet and flows away from the electrolyte inlet via the overflow.
  • An excess of electrolyte in the electrolyte feed means in the context of the present invention that the electrolyte feed is always filled evenly over the entire width at least with an electrolyte film.
  • electrolyte inlet always a certain level of electrolyte must be present over the entire width of the electrolyte inlet. This is best ensured if always a certain amount of electrolyte flows not only through the gap, but also via the overflow from the electrolyte feed.
  • the excess of the electrolyte which is removed via the overflow is 0.5 to 30% by volume, particularly preferably 1 to 20% by volume.
  • the amount of electrolyte that a falling film cell requires for its trouble-free operation depends only on the type of falling film cell, but not on the selected current densities. Therefore, the excess electrolyte must be set only once at the beginning of the electrolysis operation and only kept constant during operation.
  • the effective height ratio h to g must be selected so that the necessary for the optimal operation of the electrolytic cell electrolyte concentration in the gap.
  • the electrochemical cell according to the invention can be used for different electrolysis processes, in which at least one electrode is a gas diffusion electrode.
  • the gas diffusion electrode functions as a cathode, more preferably as an oxygen-consuming cathode, wherein the gas supplied to the electrochemical cell is an oxygen-containing gas, e.g. Air, oxygen-enriched air or oxygen itself.
  • the cell according to the invention is preferably used for the electrolysis of an aqueous solution of an alkali metal halide, in particular of sodium chloride.
  • the gas diffusion electrode is constructed, for example, as follows:
  • the gas diffusion electrode consists at least of an electrically conductive carrier and an electrochemically active coating.
  • the electrically conductive carrier is preferably a mesh, woven, braided, knitted, nonwoven or foam of metal, in particular of nickel, silver or silver-plated nickel.
  • the electrochemically active coating preferably consists of at least one catalyst, e.g. Silver (I) oxide, and a binder, e.g. Polytetrafluoroethylene (PTFE).
  • the electrochemically active coating may be composed of one or more layers.
  • a gas diffusion layer for example of a mixture of carbon and polytetrafluoroethylene, can be provided, which is applied to the support.
  • electrodes of titanium may be used, which are e.g. coated with ruthenium-iridium-titanium oxides or ruthenium-titanium oxide.
  • ion exchange membrane a commercially available membrane, e.g. from DuPont, e.g. Nafion® NX2010.
  • FIG. 1 an embodiment of an electrochemical cell according to the invention is shown in longitudinal section. Electrolyte flows out of the electrolyte reservoir 7 via an electrolyte feed line 8 into the electrolyte inlet 10 of the electrolysis half cell with gas diffusion electrode 4 (FIG. FIG. 2 ).
  • the electrolyte reservoir 7 is disposed above the electrolyte inlet 10.
  • the electrolyte feed 10 extends longitudinally over the entire width of the electrolysis half cell above the gap 11 (FIG. FIG. 2 ).
  • the height difference between the liquid level in the receiver tank 7 and the liquid level in the electrolyte inlet 10 is designated by h.
  • the electrolyte flows uniformly over the entire width of the electrolysis half-cell via the electrolyte inlet 10 into the gap 11 (FIG. FIG. 2 ). In the gap 11, the electrolyte flows down into the electrolyte outlet 20 (FIG. FIG. 2 ) leading to the gas space 5 ( FIG. 2 ), and from the electrolyte drain 20 via an electrolyte discharge 15 into an electrolyte reservoir 14.
  • the gas space 5 is terminated with a metal plate, e.g. a sheet, 23 separated from the electrolyte effluent 20.
  • a metal plate e.g. a sheet, 23 separated from the electrolyte effluent 20.
  • the oxygen pressure can thus be adjusted independently of the pressure conditions in the gap 11 and brought to optimum operating conditions for the gas diffusion electrodes. Drainage holes (not shown here) allow drainage of possibly accumulated condensate from the back of the gas diffusion electrode.
  • the electrolysis half-cell has an overflow channel 13, which in the illustrated embodiment is U-shaped, with the apex of the U-shaped channel pointing upwards.
  • an additional overflow channel 12 is provided, which is arranged substantially horizontally. Excess electrolyte, which does not flow off in the gap 11, flows via the overflow channel 12 into a side channel 21, which is arranged vertically to the side of the electrolysis half-cell and dissipates excess electrolyte downwards. Excess electrolyte is collected in the electrolyte reservoir 14.
  • the gas distribution pipe 18 thus forms the gas inlet into the electrolysis half cell.
  • Unconsumed oxygen can leave the gas space 5 via a gas line 9 as a gas outlet and flow into the electrolyte reservoir 7.
  • the electrolyte reservoir 7 also serves as a gas collection container.
  • a pump 30 is provided, which pumps electrolyte from the collecting container 14 into the storage container 7.
  • FIG. 2 shows the electrolytic cell according to FIG. 1 in cross section. It consists of an anode half-cell 1 with an anode 6 and a cathode half-cell 22 with a gas diffusion electrode 4 as a cathode.
  • the two half-cells 1, 22 are separated from each other by an ion exchange membrane 3. Between the ion exchange membrane 3 and the gas diffusion electrode 4 there is a gap 11. Behind the gas diffusion electrode 4, a gas space 5 is arranged. The gas space 5 thus forms the rear space behind the gas diffusion electrode 4.
  • electrolyte flows from the electrolyte inlet 10 into the gap 11 and from the gap 11 in the electrolyte effluent 20 until the electrolyte is finally collected via the electrolyte discharge 15 in the electrolyte reservoir 14.
  • Gas which flows via the gas distribution pipe 18 into the gas space 5, can flow via the gas outlet 9 into the electrolyte reservoir 7 above the electrolytic cell.
  • a metal plate 23 separates the gas space 5 from the electrolyte outlet 20.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Claims (10)

  1. Cellule électrochimique, constituée par au moins une demi-cellule anodique (1) contenant une anode (6), une demi-cellule cathodique (22) contenant une cathode (4), et une membrane échangeuse d'ions (3) agencée entre la demi-cellule anodique (1) et la demi-cellule cathodique (22), l'anode (6) et/ou la cathode (4) étant une électrode à diffusion de gaz, une fente (11), une alimentation d'électrolyte (10) au-dessus de la fente (11) et une évacuation d'électrolyte (20) en dessous de la fente (11), ainsi qu'une entrée de gaz (18) et une sortie de gaz (9) étant agencées entre l'électrode à diffusion de gaz (4) et la membrane échangeuse d'ions (3), caractérisée en ce que l'alimentation d'électrolyte (10) est raccordée avec un contenant de stockage d'électrolyte (7) par une conduite d'alimentation en électrolyte (8) et comprend un trop-plein, le trop-plein étant configuré sous la forme d'un canal de trop-plein (12 ; 13) et la pression dans l'alimentation d'électrolyte (10) pouvant être ajustée par le choix de la hauteur g du canal de trop-plein.
  2. Cellule électrochimique selon la revendication 1, caractérisée en ce que le contenant de stockage d'électrolyte (7) est agencé 30 à 200 cm au-dessus de l'alimentation d'électrolyte (10).
  3. Cellule électrochimique selon la revendication 1, caractérisée en ce que le contenant de stockage d'électrolyte (7) est raccordé avec l'alimentation d'électrolyte (10) par une pompe.
  4. Cellule électrochimique selon l'une quelconque des revendications 1 à 3, caractérisée en ce que la hauteur du trop-plein est de 0 à 190 cm.
  5. Cellule électrochimique selon la revendication 1, caractérisée en ce que le canal de trop-plein est un canal en forme de U (13), dont le sommet est orienté vers le haut.
  6. Cellule électrochimique selon la revendication 1, caractérisée en ce que le canal de trop-plein est configuré sous la forme d'un tube vertical ou d'un puits.
  7. Cellule électrochimique selon l'une quelconque des revendications 1 à 6, caractérisée en ce que la sortie de gaz (9) est raccordée avec le contenant de stockage d'électrolyte (7).
  8. Cellule électrochimique selon l'une quelconque des revendications 1 à 6, caractérisée en ce que la sortie de gaz (9) est raccordée avec un contenant de collecte de gaz et l'espace de gaz (5) est isolé de la fente (11) .
  9. Procédé d'électrolyse d'une solution aqueuse d'halogénure alcalin dans une cellule électrochimique selon l'une quelconque des revendications 1 à 8, caractérisé en ce que l'électrolyte est introduit depuis le contenant de stockage d'électrolyte (7) en excès dans l'alimentation d'électrolyte (10), l'électrolyte s'écoule depuis l'alimentation d'électrolyte (10) dans la fente (11) et depuis la fente (11) dans l'évacuation d'électrolyte (20), et est évacué depuis l'alimentation d'électrolyte (10) par le trop-plein.
  10. Procédé selon la revendication 9, caractérisé en ce que l'excès d'électrolyte est de 0,5 à 30 % en volume, de préférence de 1 à 20 % en volume.
EP05732004.6A 2004-04-17 2005-04-09 Cellule electrochimique Active EP1740739B1 (fr)

Applications Claiming Priority (2)

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DE102004018748A DE102004018748A1 (de) 2004-04-17 2004-04-17 Elektrochemische Zelle
PCT/EP2005/003756 WO2005100640A1 (fr) 2004-04-17 2005-04-09 Cellule electrochimique

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EP1740739A1 EP1740739A1 (fr) 2007-01-10
EP1740739B1 true EP1740739B1 (fr) 2019-06-26

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US (1) US8247098B2 (fr)
EP (1) EP1740739B1 (fr)
JP (1) JP4990127B2 (fr)
CN (1) CN1969061B (fr)
DE (1) DE102004018748A1 (fr)
DK (1) DK1740739T3 (fr)
HK (1) HK1106558A1 (fr)
TW (1) TWI359523B (fr)
WO (1) WO2005100640A1 (fr)

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DE102011100768A1 (de) 2011-05-06 2012-12-06 Bayer Material Science Ag Elektrochemische Zelle mit Rahmendichtung zur alternativen Abdichtung gegenRandläufigkeiten des Elektrolyten
GB2539478B (en) 2015-06-17 2017-11-22 Siemens Ag Electrochemical cell and process
KR101802749B1 (ko) * 2016-10-20 2017-12-28 주식회사 에이치투 캐필러리 튜브를 포함한 흐름전지 스택
KR102086386B1 (ko) * 2016-11-14 2020-03-10 주식회사 미트 금속 연료 전지 및 금속 연료 시스템
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JP2007532777A (ja) 2007-11-15
US8247098B2 (en) 2012-08-21
WO2005100640A1 (fr) 2005-10-27
HK1106558A1 (en) 2008-03-14
US20050277016A1 (en) 2005-12-15
DE102004018748A1 (de) 2005-11-10
TWI359523B (en) 2012-03-01
EP1740739A1 (fr) 2007-01-10
CN1969061B (zh) 2010-12-15
TW200607143A (en) 2006-02-16
DK1740739T3 (da) 2019-09-23
JP4990127B2 (ja) 2012-08-01
CN1969061A (zh) 2007-05-23

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