EP0082643A2 - Elektrodenaufbau für Elektrolysezellen - Google Patents

Elektrodenaufbau für Elektrolysezellen Download PDF

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Publication number
EP0082643A2
EP0082643A2 EP82306578A EP82306578A EP0082643A2 EP 0082643 A2 EP0082643 A2 EP 0082643A2 EP 82306578 A EP82306578 A EP 82306578A EP 82306578 A EP82306578 A EP 82306578A EP 0082643 A2 EP0082643 A2 EP 0082643A2
Authority
EP
European Patent Office
Prior art keywords
electrode
current
collector
electrode structure
electrolyser
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
Application number
EP82306578A
Other languages
English (en)
French (fr)
Other versions
EP0082643B1 (de
EP0082643A3 (en
Inventor
Christopher T. Bowen
John H. Davis
Rodney L. Leroy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Electrolyser Inc
Original Assignee
Electrolyser Corp Ltd
Noranda Inc
Electrolyser Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Electrolyser Corp Ltd , Noranda Inc, Electrolyser Inc filed Critical Electrolyser Corp Ltd
Publication of EP0082643A2 publication Critical patent/EP0082643A2/de
Publication of EP0082643A3 publication Critical patent/EP0082643A3/en
Application granted granted Critical
Publication of EP0082643B1 publication Critical patent/EP0082643B1/de
Expired legal-status Critical Current

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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
    • 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

Definitions

  • This invention relates to an electrode structure for electrolyser cells, more particularly of the unipolar type.
  • the voltage of an electrolytic cell is the sum of three major components: the thermodynamic potential required for the overall cell reaction; the electrode overvoltages which result from kinetic limitations; and a resistive contribution to cell voltage.
  • the major avenues open for reduction of energy requirements are electrode activation to reduce the overvoltages for the desired reactions, and design improvement to reduce resistive losses.
  • Resistive losses are of two types: ionic, reflecting a resistance to the passage of current in the electrolyte; and electronic, reflecting the resistance to the passage of current in current-carrying metallic components of the electrolyser.
  • ionic reflecting a resistance to the passage of current in the electrolyte
  • electronic reflecting the resistance to the passage of current in current-carrying metallic components of the electrolyser.
  • bipolar electrolyser designs the ionic resistance contribution is of overwhelming importance, since current paths through metallic elements are normally very short in length.
  • electronic resistance losses can become substantial, as the electronic current is normally removed from each electrode to a current-removal structure.
  • Typical pre-electrode forms are perforated plates, expanded-metal sheet, and woven metal cloth. Any suitably-porous structure can be envisaged, including grooved sheets on foam metal.
  • Canadian Patent 1,002,476 issued December 28, 1976 discloses the use of a thin corrugated structure, internal to the pre-electrode, to provide a spring effect and improve the compression of anode/separator/cathode array while allowing for flexibility during cell assembly.
  • Canadian Patent 1,086,256, issued September 23, 1980 features the use of a similar internal structure for the purpose of providing support to the pre-electrode when a diaphragm material is being deposited on the electrode surfaces under vacuum.
  • the internal support structure of these electrodes is not connected to current removal structures and, more importantly, not designed to carry currents in the order of 1000 to 10,000 amperes or more, such as required in industrial unipolar electrolyser cells.
  • the pre-electrode elements are often attached to central current-collector structures, for example rods or an equivalent fabricated structure in the unipolar design as disclosed in Canadian Patent 1,041,040, issued October 24, 1978, or a formed bipolar plate in bipolar electrolyser equipment, as disclosed in U.S. Patent 3,379,634, issued April 23, 1968.
  • These electrode designs are, however, not adequate for electrolyser cells because they do not allow efficient removal of gases up the electrode.
  • electrolyser cells would require a large number of current conductive rods in order for the pre-electrodes to carry currents in the order of 1000 to 10,000 amperes and more, and this would unduly restrict gas circulation between the porous pre-electrodes.
  • the electrode structure in accordance with the present invention, comprises a central current-collector structure having high points on at least one side thereof and adapted to be placed vertically in the electrolytic cell, and a porous electrode secured to the high points of the current-collector structure on at least one side thereof so as to form an essentially-planar pre-electrode surface.
  • the high points of the current-collector structure are located on the central current-collector so as to allow an unimpeded rise of the evolved gases to the top of the electrode.
  • the central current-collector is preferably a plate having vertically oriented corrugations and the pre-electrode is secured to the crest of such corrugations.
  • a gas evolving electrode 10 anode or cathode which comprises a central current collector 12 to each side of which is attached a pre-electrode 14. Ionic current flow from the adjacent electrode or electrodes of opposite polarity would flow to the electrode perpendicular to the pre-electrode structures, as shown by arrows A, and current is removed from the pre-electrodes by the current collector 12, as indicated by arrow B.
  • the pre-electrodes are normally woven screen, expanded metal, or perforated plate but can be of any other perforated or porous geometry which allows for gas passage through the structure to the interior of the electrode.
  • the central current-collector is a solid, formed metal piece which is illustrated as being corrugated, although any structure which could be formed in an economic manner, and which allows for unimpeded rise of the evolved gases to the top of the electrode, would be within the scope of the invention.
  • the pre-electrode is attached to the central current collector at the high points of the structure so as to form an essentially-planar pre-electrode surface.
  • the attachment may be by a weld, by screws or other mechanical fasteners, or by pressure which is exerted by the composite electrode/separator mass.
  • the central current collector must be attached to the elements removing current from the electrode. This attachment may be continuous, through a welded, bolted, or riveted contact, or it may be at several points through connections to suitable conductors. In this latter case, additional current-conducting material may be included in the structure, as indicated by bar 16, to assist current equalization in the vertical direction, to further minimize resistive losses.
  • the parameters of the electrode of this invention are established by an optimization which considers the resistive losses in the structure, the cost of the material of construction, and the physical constraints imposed by the detailed electrolyser design on maximum and minimum electrode thickness. It has been surprisingly found that a depth of the corrugations C (Figure 2) as low as 0.16 cm is satisfactory for electrode heights as great as 75 cm, with gas evolution at current densities to 1,000 mA/cm'; no increase in the ionic-resistance factor of the electrolyser was detectible with increasing current density, suggesting that the product gas is being effectively removed to the interior of the electrode structure. However, the depth of corrugations would likely not be less than 0.1 cm. The maximum depth of corrugation would be established by practical constraints on electrolyser size; it would be unlikely that a depth of corrugation greater than 3 cm would be desirable.
  • the thickness D ( Figure 2) of the current collector material may be between .04 and 1.5 cm depending on the amount of current to be removed from the electrode.
  • the length E ( Figure 2) of the corrugation waves, or the spacing of the high points of equivalent formed structures, will be the minimum consistent with economic forming of the current-collector material. This is necessary to minimize resistance losses in the pre-electrode structure.
  • the length of corrugation might be between 0.7 and 15 cm for a current-collector material having a thickness of between 0.04 and 1.5 cm.
  • Each of the major electrode parameters can be optimized in this way: thickness of the material from which the current collector is formed, width of the electrode, and, depending on the detailed method being used for current removal, dimensions of the current equalization or removal bar 16 and the electrode height.
  • Figures 3 and 4 illustrate a typical optimization, for an electrode from which current is being removed uniformly at the side.
  • the anode and cathode are assumed to be of similar design.
  • the contribution to cell voltage due to electronic resistance of the current-collector structure diminishes as the thickness of the current-collector material is increased, or as the width of the electrode is reduced.
  • Such voltage contributions can be calculated unambiguously by the method described by R.O. Loutfy and R.L. LeRoy in the Journal of Applied Electrochemistry 8 (1978) pages 549-555.
  • the results presented assume that the material of construction is 0 mild steel at 70 C, and that the current density on the projected pre-electrode structure is 240 mA/cm 2.
  • Figure 4 shows a typical optimization, in this case assuming a current price for mild steel and a power cost of $0.03/kWh.
  • the optimum electrode thickness is seen to increase with increasing electrode width.
  • the optimum values indicated by calculations such as these will have to be modified based on other considerations related to the overall dimensions of the electrolyser, the method of current removal, etc.
  • the formed current-collector structures of this invention are in no way related to formed structures described in the prior art, which have been used for mechanical purposes such as compression of the electrode mass.
  • the electrodes of this invention are designed to carry currents of 1,000 to 10,000 amperes and more, and precise specification of the current-removal provisions is essential to achieve an economic result.
  • the massive quantities of gas evolved at such current loadings must be free to move unimpeded up the electrode to escape at the top. None of the proposals of the prior art accomplish these two objectives.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP82306578A 1981-12-23 1982-12-09 Elektrodenaufbau für Elektrolysezellen Expired EP0082643B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CA000393106A CA1171817A (en) 1981-12-23 1981-12-23 Electrode structure for electrolyser cells
CA393106 1981-12-23

Publications (3)

Publication Number Publication Date
EP0082643A2 true EP0082643A2 (de) 1983-06-29
EP0082643A3 EP0082643A3 (en) 1983-09-14
EP0082643B1 EP0082643B1 (de) 1987-11-04

Family

ID=4121691

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82306578A Expired EP0082643B1 (de) 1981-12-23 1982-12-09 Elektrodenaufbau für Elektrolysezellen

Country Status (6)

Country Link
EP (1) EP0082643B1 (de)
JP (1) JPS608310B2 (de)
BR (1) BR8207435A (de)
CA (1) CA1171817A (de)
DE (1) DE3277587D1 (de)
ZA (1) ZA829414B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0357143A2 (de) * 1988-09-02 1990-03-07 Metallgesellschaft Ag Gasdiffusionselektrode
WO2021197787A1 (de) * 2020-04-01 2021-10-07 Siemens Aktiengesellschaft Vorrichtung und verfahren zur kohlenstoffdioxid- oder kohlenstoffmonoxid-elektrolyse

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08199726A (ja) * 1995-01-31 1996-08-06 Daiwa Danchi Kk 木造建築物の天井パネルの取り付け構造

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH331199A (de) * 1955-04-01 1958-07-15 Lonza Ag Bipolare Elektrode für Druckelektrolyseure der Filterpressen-Bauart
US3925886A (en) * 1974-01-03 1975-12-16 Hooker Chemicals Plastics Corp Novel cathode fingers
US3941675A (en) * 1971-09-28 1976-03-02 Friedrich Uhde Gmbh Bipolar multiple electrolytic cell comprising a diaphragm and electrode for same
DE2632073A1 (de) * 1976-07-16 1978-01-19 Schlemmer Fa Manfred Akkumulator
US4124482A (en) * 1974-11-22 1978-11-07 Knight Bill J Method and apparatus for casting anodes
GB2001347A (en) * 1977-07-20 1979-01-31 Imp Metal Ind Kynoch Ltd Electrode and hanger bar therefor
FR2433592A1 (fr) * 1978-07-27 1980-03-14 Oronzio De Nora Impianti Cellule d'electrolyse et procede de production d'halogenes
US4210516A (en) * 1978-05-19 1980-07-01 Hooker Chemicals & Plastics Corp. Electrode element for monopolar electrolysis cells

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH331199A (de) * 1955-04-01 1958-07-15 Lonza Ag Bipolare Elektrode für Druckelektrolyseure der Filterpressen-Bauart
US3941675A (en) * 1971-09-28 1976-03-02 Friedrich Uhde Gmbh Bipolar multiple electrolytic cell comprising a diaphragm and electrode for same
US3925886A (en) * 1974-01-03 1975-12-16 Hooker Chemicals Plastics Corp Novel cathode fingers
US4124482A (en) * 1974-11-22 1978-11-07 Knight Bill J Method and apparatus for casting anodes
DE2632073A1 (de) * 1976-07-16 1978-01-19 Schlemmer Fa Manfred Akkumulator
GB2001347A (en) * 1977-07-20 1979-01-31 Imp Metal Ind Kynoch Ltd Electrode and hanger bar therefor
US4210516A (en) * 1978-05-19 1980-07-01 Hooker Chemicals & Plastics Corp. Electrode element for monopolar electrolysis cells
FR2433592A1 (fr) * 1978-07-27 1980-03-14 Oronzio De Nora Impianti Cellule d'electrolyse et procede de production d'halogenes

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0357143A2 (de) * 1988-09-02 1990-03-07 Metallgesellschaft Ag Gasdiffusionselektrode
EP0357143A3 (en) * 1988-09-02 1990-05-16 Metallgesellschaft Ag Gas diffusion electrode
WO2021197787A1 (de) * 2020-04-01 2021-10-07 Siemens Aktiengesellschaft Vorrichtung und verfahren zur kohlenstoffdioxid- oder kohlenstoffmonoxid-elektrolyse

Also Published As

Publication number Publication date
JPS58151484A (ja) 1983-09-08
BR8207435A (pt) 1983-10-18
EP0082643B1 (de) 1987-11-04
DE3277587D1 (en) 1987-12-10
ZA829414B (en) 1983-10-26
EP0082643A3 (en) 1983-09-14
CA1171817A (en) 1984-07-31
JPS608310B2 (ja) 1985-03-01

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