EP2851453A1 - Metallplatte für Elektrode sowie Elektrode - Google Patents

Metallplatte für Elektrode sowie Elektrode Download PDF

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Publication number
EP2851453A1
EP2851453A1 EP14002711.1A EP14002711A EP2851453A1 EP 2851453 A1 EP2851453 A1 EP 2851453A1 EP 14002711 A EP14002711 A EP 14002711A EP 2851453 A1 EP2851453 A1 EP 2851453A1
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EP
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Prior art keywords
electrode
metal plate
conductance
fine irregular
irregular surface
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EP14002711.1A
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English (en)
French (fr)
Inventor
Akira Narai
Norikazu Matsukura
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Kobe Steel Ltd
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Kobe Steel Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers

Definitions

  • the present invention relates to a metal plate for an electrode and an electrode used in electrolysis.
  • platinized titanium plates are generally used as an electrode material from a viewpoint of its low overvoltage, low elution property, the cost, and so forth.
  • a structure has been proposed (Japanese Patent No. 3467954 ). In this structure, an irregularity portion having a height of 0.5 mm or more is formed on a discharging surface of an electrode for electrolysis.
  • the present invention has been proposed in view of the above-described situation, and an object of the present invention is to provide a metal plate for an electrode and an electrode used in electrolysis of high electrolysis efficiency.
  • a metal plate for an electrode according to the present invention is a metal plate for an electrode used in electrolysis performed in an aqueous solution or an organic solvent.
  • the metal plate for an electrode includes a fine irregular surface.
  • a ratio Ra/Pc of the fine irregular surface which is a ratio of an arithmetic mean roughness Ra in ⁇ m to a peak count Pc in counts/mm, is equal to or more than 0.8.
  • the irregularities of the electrode surface inhibit the flow of electrolyte solution near the electrode, thereby obstructing transportation of ions involved in a reaction.
  • the flow of the electrolyte solution is changed near this electrode. This varies the degree with which the transportation of the ions is obstructed, and accordingly, the conductance varies.
  • the ratio Ra/Pc correlates with the amount of the ions, the transportation of which is obstructed by the inhibition of the flow of the electrolyte solution near the electrode, that is, the conductance.
  • the metal plate for an electrode includes the fine irregular surface, of which the ratio Ra/Pc is equal to or more than 0.8, a high conductance is obtained, and accordingly, electrolysis efficiency in electrolysis using the metal plate for an electrode is improved.
  • a maximum height roughness Rz of the fine irregular surface is preferably equal to or less than 50 ⁇ m.
  • the maximum height roughness Rz of the fine irregular surface exceeds the above-described upper limit, it is difficult to form irregularities, the intervals of which between adjacent peaks or valleys are further reduced, in the fine irregular surface.
  • the maximum height roughness Rz of the fine irregular surface is equal to or less than the above-described upper limit, the electrolysis efficiency in the electrolysis using the metal plate for an electrode is further improved.
  • the arithmetic mean roughness Ra of the fine irregular surface is preferably from 3.6 to 10 ⁇ m.
  • the arithmetic mean roughness Ra of the fine irregular surface is less than the above-described lower limit, it is difficult to increase the ratio Ra/Pc.
  • the arithmetic mean roughness Ra of the fine irregular surface exceeds the above-described upper limit, the peak count Pc of the fine irregular surface tends to increase. Thus, it is difficult to increase the ratio Ra/Pc.
  • the arithmetic mean roughness Ra of the fine irregular surface is within the above-described range, a high conductance can be reliably obtained, and accordingly, the electrolysis efficiency in the electrolysis using the metal plate for an electrode is further improved.
  • the peak count Pc of the fine irregular surface is preferably from 0.5 to 5 counts/mm.
  • the peak count Pc of the fine irregular surface exceeds the above-described upper limit, it is difficult to increase the ratio Ra/Pc.
  • the peak count Pc of the fine irregular surface is less than the above-described lower limit, the arithmetic mean roughness Ra of the fine irregular surface tends to decrease. Thus, it is difficult to increase the ratio Ra/Pc.
  • the peak count Pc of the fine irregular surface is within the above-described range, a high conductance can be reliably obtained, and accordingly, the electrolysis efficiency in the electrolysis using the metal plate for an electrode is further improved.
  • the fine irregular surface of the metal plate for an electrode preferably has irregularities that form a periodical geometric pattern.
  • the fine irregular surface has the irregularities that form periodical geometric pattern, compared to the case of random irregularities, the obtained conductance can be increased, and accordingly, the electrolysis efficiency in the electrolysis using the metal plate for an electrode is reliably improved.
  • the irregularities of the metal plate for an electrode are preferably formed by rolling.
  • the metal plate for an electrode by which a high conductance can be obtained, can be easily fabricated, and the cost of an electrode for electrolysis can be reduced.
  • the metal plate for an electrode preferably contains titanium as the principal component. Since titanium has a good chemical resistance and is unlikely to be corroded, by containing the titanium as the principal component of the metal plate for an electrode, a stable electrolysis process is performed even when an electrolyte solution having a high reactivity permeates the plating of an electrode, which is formed of titanium and plated with a precious metal, through pinholes.
  • the electrode is preferably formed of the above-described metal plate for an electrode.
  • the electrode formed of the above-described metal plate for an electrode allows the electrolysis efficiency in the electrolysis to be improved compared to that achieved by the related-art electrode.
  • the above-described arithmetic mean roughness Ra and the maximum height roughness Rz are measured with the cut-off value ⁇ c of 0.8 mm in conformity with Japanese Industrial Standards (JIS) B 0601:2001.
  • the above-described peak count Pc is measured with the cut-off value of 0.8 mm, the cut-off ratio of 300, and the peak count level 2H of 1 ⁇ m in conformity with the International Organization for Standardization (ISO) standard 4288-1998.
  • the electrode formed of the metal plate for an electrode according to the present invention has a high conductance.
  • electrolysis efficiency is improved by using the metal plate for an electrode according to the present invention.
  • a metal plate for an electrode according to an embodiment used in electrolysis is used in electrolysis performed in an aqueous solution or an organic solvent and has a fine irregular surface.
  • the ratio Ra/Pc of the arithmetic mean roughness Ra (in ⁇ m) to the peak count Pc (in counts/mm) of this irregular surface is equal to or more than 0.8.
  • the inventors have found that the conductance obtained by an electrode formed of a metal plate for an electrode varies depending on the shape of a surface of the metal plate for an electrode contributing to electrolysis and that the ratio Ra/Pc of the arithmetic mean roughness Ra (in ⁇ m) to the peak count Pc (counts/mm) of the electrode surface correlates to the conductance as illustrated in Fig. 1 .
  • Fig. 1 illustrates a multiple regression line obtained as follows: surface profiles of a plurality of metal plates for an electrode, the surface of which have different irregularities, were measured; the metal plates for an electrode were platinized and used as the electrodes; the I-V characteristics during electrolysis were measured and the conductance was obtained; and the measured results were subjected to a multiple regression analysis.
  • the arithmetic mean roughnesses Ra and the peak counts Pc were measured under the following conditions: the cut-off value ⁇ c is 800 ⁇ m, the cut-off ratio is 300, the measurement length is 4 mm, the measurement speed is 0.6 mm/second, and the peak count level 2H is 1 ⁇ m.
  • the plurality of titanium plates were platinized so as to make electrodes, which was subjected to electrolysis where the platinized electrodes were used as counter electrodes.
  • the peak count refers to a total count counted as follows: an upper peak count level, which is 1 ⁇ m separated from the center line of the roughness curve of the titanium plate surface at a peak count level (2H), is set, and when there are two intersections of the upper peak count level and the roughness curve, it is counted as a peak.
  • the conductance is about 0.030 G/cm 2 when a mirror-finished platinum plate is used as the electrode.
  • the conductance is equal to or more than 0.035 G/cm 2 in accordance with the multiple regression line illustrated in Fig. 1 . From this, it can be understood that a conductance higher than that of a smooth electrode (mirror-finished platinum plate electrode) can be obtained. That is, by forming the irregularities in the surface, of which the above-described ratio Ra/Pc is equal to or more than 0.8, a metal plate for an electrode, by which a high conductance can be obtained, can be made.
  • the surface area is larger than the apparent electrode area.
  • the conductance obtained by such a platinized electrode plate may be less than the conductance obtained by a smooth electrode (mirror-finished platinum electrode), the surface area of which is substantially equal to its apparent surface area, depending on the shape of the irregularities. From this finding, the inventors have found that the increase in the surface area due to the irregularities of the electrode surface does not necessarily contribute to an increase in the conductance.
  • the inventors thought that a platinized electrode having irregularities on its surface and by which a larger conductance than that obtained by a smooth electrode (mirror-finished platinum electrode) has a substantially optimum structure of irregularities and is highly efficient.
  • the inventors have subsequently found the parameter for irregularities relating to the conductance as described above with reference to the conductance obtained by the smooth electrode.
  • electrode reaction occurs in electrolysis as follows: that is, ions move in an electrolyte solution, are activated near a surface of an electrode, and exchange charges on the electrode.
  • Figs. 2A and 2B are conceptual views of the electrode reaction.
  • Fig. 2A illustrates a state of a potential E near an electrode interface.
  • Fig. 2B is an enlarged conceptual view of part of an electric double layer 3 near an electrode 1 in Fig. 2A .
  • dipoles 5 are formed of the ions attracted by the potential of the electrode 1 near the electrode 1, the potential E of the electrode linearly changes in a Helmholtz layer 6 immediately adjacent to the electrode 1. Alignment of the dipoles 5 are gradually disturbed on a side further from the electrode 1 than the Helmholtz layer 6. Thus, the potential E gently reduces in a Gouy-Chapman layer 7. On a side further from the electrode 1 than the Gouy-Chapman layer 7, charges of ions having positive charges and charges of ions having negative charges cancel out one another, thereby maintaining an electrically neutral state. In general, in a size larger than a length represented by a Debye length, positive and negative charges cancel out one another. Thus, the state is generally neutral and there is no effect of the potential of the electrode 1.
  • the electric double layer 3 is generally several to 50 times thicker than an atom or a molecule. Ions contributing to the reaction are not affected by the electrical attractive force until they reach the electric double layer 3.
  • a diffusion layer 4 of 10 -3 cm or less is provided on a side further from the electrode 1 than the electric double layer 3.
  • the diffusion of ions in the diffusion layer 4 is controlled mainly by random motions and follows the Stokes-Einstein Relationship.
  • a diffusion coefficient representing the diffusion is a function of the viscosity of the electrolyte, the temperature of the solution, and the diameter of the ions. Considering that electrolysis is typically performed at a constant temperature, the diffusion coefficient is the function of the viscosity of the electrolyte.
  • the ions contributing to the electrode reaction move from a convection and diffusion region 2 located further away from the electrode 1 than the diffusion layer 4.
  • the ions are affected by voluntary stirring due to, for example, the convection of the electrolyte solution and forced bubbles.
  • the ion concentration of the diffusion layer 4 is changed by the electrode reaction, and accordingly, a concentration gradient of the ions is formed, thereby facilitating the diffusion.
  • speeds of reactions including the diffusion of the ions toward the electrode need to be increased in every reacting path.
  • the lower limit of the ratio Ra/Pc of the arithmetic mean roughness Ra (in ⁇ m) to the peak count Pc (counts/mm) is more preferably 1.2.
  • the upper limit of the above-described ratio Ra/Pc is preferably 4.
  • the ratio Ra/Pc is equal to or more than the above-described lower limit, a high conductance of 0.37 G/cm 2 or more can be obtained by a titanium plate, and the conductance can be increased after the titanium plate has been platinized.
  • the ratio Ra/Pc exceeds the upper limit, it is difficult to form a fine irregular surface having a shape, by which such a high conductance can be obtained. This may lead to an increase in the production cost.
  • the upper limit of the maximum height roughness Rz of the above-described fine irregular surface is preferably 50 ⁇ m, and more preferably 40 ⁇ m.
  • the maximum height roughness Rz of the fine irregular surface exceeds the upper limit, it is difficult to form irregularities in which intervals between adjacent peaks or valleys are further reduced. As a result, the conductance obtained by the metal plate for an electrode cannot be further improved.
  • the lower limit of the arithmetic mean roughness Ra of the fine irregular surface is preferably 3.6 ⁇ m, and more preferably 4 ⁇ m.
  • the upper limit of the arithmetic mean roughness Ra of the fine irregular surface is preferably 10 ⁇ m, and more preferably 7 ⁇ m.
  • the arithmetic mean roughness Ra of the fine irregular surface is less than the lower limit, it is difficult to increase the ratio Ra/Pc, and accordingly, the conductance obtained by the metal plate for an electrode cannot be improved.
  • the arithmetic mean roughness Ra of the fine irregular surface exceeds the upper limit, the peak count Pc of the fine irregular surface tends to increase. Thus, it is difficult to increase the ratio Ra/Pc, and accordingly, the conductance obtained by the metal plate for an electrode cannot be improved.
  • the lower limit of the peak count Pc of the fine irregular surface is preferably 0.5 counts/mm, and more preferably 1.5 counts/mm.
  • the upper limit of the peak count Pc of the fine irregular surface is preferably 5 counts/mm, and more preferably 4.5 counts/mm.
  • the peak count Pc of the fine irregular surface exceeds the upper limit, it is difficult to increase the ratio Ra/Pc, and accordingly, the conductance obtained by the metal plate for an electrode cannot be improved.
  • the peak count Pc of the fine irregular surface is less than the lower limit, the arithmetic mean roughness Ra of the fine irregular surface tends to decrease. Thus, it is difficult to increase the ratio Ra/Pc, and accordingly, the conductance obtained by the metal plate for an electrode cannot be improved.
  • irregularities of the fine irregular surface irregularities that form a periodical geometric pattern are desirable compared to random irregularities.
  • the solution regularly flows near the electrode surface, and accordingly, obstruction of transportation of ions near the electrode surface is reduced.
  • the ions are activated near the electrode surface, thereby reliably improving the conductance.
  • the material of the electrode may be a material other than titanium.
  • the material of the electrode may be tantalum, niobium, zirconium, hafnium, vanadium, molybdenum, tungsten, or an alloy of any of these materials.
  • the electrode material may be plated with a precious metal other than platinum.
  • the electrode material may be gold-plated or rhodium-plated.
  • the irregularities of the surfaces and the conductances of the sample electrodes according to the first to third examples and the first comparative example were measured.
  • the conductances were measured by performing an electrolysis experiment.
  • the irregularities of the surfaces of these samples were measured with a surface roughness tester (SURFCOM 130A by TOKYO SEIMITSU CO., LTD.).
  • the arithmetic mean roughnesses Ra (in ⁇ m) and the peak counts Pc (in counts/mm) of the surfaces of the sample electrodes were measured under the following conditions: the cut-off value ⁇ c is 800 ⁇ m, the cut-off ratio is 300, the measurement length is 4 mm, the measurement speed is 0.6 mm/second, and the peak count level 2H is 1 ⁇ m.
  • each sample electrode was masked by polyimide tape with a 10 mm x 10 mm region of the surface of the sample electrode exposed from the mask.
  • a ⁇ 0.5 mm stainless steel wire formed of a stainless steel specified as Steel Use Stainless (SUS) 304 in the Japanese Industrial Standards was firmly wound around each of the sample electrodes, and secured by crimping. Junctions with copper wires were sealed by epoxy resin (by Stycast 2057 and Catalyst 11 by Henkel Japan Ltd.).
  • a 3-liter beaker was filled with an electrolyte solution containing 3.5 percent by mass of NaCl conforming to Japanese pharmacopoeia.
  • the sample electrodes opposed counter electrodes (platinized) in the electrolyte solution such that a 10-mm gap was set between each of the sample electrodes and a corresponding one of the counter electrodes.
  • 105.0 g of NaCl was put into the 3-liter beaker, and after that, pure water was poured into the beaker to the measurement mark to dissolve the NaCl in the pure water.
  • a stirrer and a diaphragm pump were used to spray the electrolyte solution onto the electrode surface and stir the electrolyte solution.
  • a power unit was programmed so as to perform a sweep from 0 to 5 V in about 13 seconds. At this time, the electrode voltage and the current were measured with a data logger. The current was measured from the voltage of a shunt resistor connected to circuitry. The conductance of the electrolyte solution was measured before and after the measurement so as to confirm that the electrolyte solution was not significantly changed by the electrolysis.
  • Table 1 shows results of the measurement of the surface profiles and results of the measurement in the electrolysis experiment of the sample electrodes according to the first to third examples and the first comparative example. Table 1 also shows the ratios Ra/Pc of the examples and the comparative example. Table 1 Sample name Ra ( ⁇ m) Pc (counts/mm) Ra/Pc Conductance (G/cm 2 ) First example 4.0 1.75 2.29 0.043 Second example 5.4 3.75 1.44 0.040 Third example 3.7 4.50 0.82 0.038 First comparative example 3.5 6.00 0.58 0.031
  • a high conductance can be obtained by each of the sample electrodes according to the first to third examples.
  • the conductance obtained by the electrode of the first example, which has periodical irregularities, is higher than the conductances obtained by the electrodes of the second and the third examples, which have random irregularities.
  • the inventors fabricated a plurality of titanium plates, the surfaces of which have different irregularities, on the basis of the above-described electrolysis model.
  • Sample electrodes were made by platinizing these titanium plates and subjected to electrolysis in an NaCl solution.
  • the conductances of the electrodes were obtained from the electrolytic characteristics measured in this electrolysis, and the dependency of the conductance on the structure of the irregularities was studied.
  • the surface areas and the conductances of the metal plates for an electrode, the surfaces of which have different irregularities were measured. Electrodes were made by platinizing titanium plates in a pinhole free manner, and a plurality of metal plates for an electrode, the surfaces of which have different irregularities, are fabricated. The surface areas and the conductance of these metal plates for an electrode were measured.
  • the above-described irregularities formed on the electrode surfaces were the following four types: periodical irregularities having the maximum height roughnesses Rz of the irregularities of 15 ⁇ m and 30 ⁇ m; and random irregularities formed of high and low steps made by machining with reduction rollers, the surfaces of which were made by electrical discharge machining.
  • the periodical irregularities formed here may be referred to as embossed structures hereafter.
  • the I-V characteristics were measured while changing the applied voltage from 0 to 5 V in about 13 seconds with a programmable power unit, thereby obtaining the conductances.
  • the surface areas of the metal plates for an electrode were measured by a confocal laser scanning microscope (OLS31-SU by Olympus Corporation). Thus, the relationships between the surface areas and the conductances were evaluated.
  • the surface area of the metal plate for an electrode is increased.
  • the reason for this is as follows: that is, by increasing the surface area of the metal plate for an electrode, it is thought that many charges for reactions can be imparted.
  • the conductances are reduced in some cases despite the increase in the surface areas.
  • the reason for this is that the irregularities for increasing the surface area are assumed to inhibit diffusion of active species near the surface of the electrode.
  • the surface area of the electrode is not only the parameter that determines conductance.
  • a non-platinized pure titanium plate and a platinized titanium plate were used as electrodes and the I-V characteristics of these electrodes were measured. The relationships among the characteristics of the titanium plate electrode and the platinized electrode were studied.
  • the pure titanium plate and the platinized titanium plate used as sample electrodes were made to have a size of 1 cm x 1 cm, and a 2 cm x 2 cm platinized titanium plate was used as a counter electrode.
  • a slight electrolytic current flows from about 1.1 V, and then, the current significantly increases from about 2.1 V
  • an electrolytic current flows from about 1.7 V, and then, the current steeply rises from about 3.5 V.
  • the reason for this is that, in the case of the titanium plate electrode, such a degree of a potential that cuts the bonding between hydrogen and titanium (over voltage) needs to be applied in order to start electrolysis.
  • a current change amount with respect to the voltage change in the titanium plate electrode after the electrolysis has started substantially coincides with a current change amount with respect to the voltage change in the platinized electrode.
  • a change in the conductance of the titanium plate electrode after the electrolysis has started correlates to a change in the conductance of the platinized electrode.
  • Fig. 4A illustrates the relationships among the arithmetic mean roughnesses Ra and the conductances in the fine irregular surfaces of the sample electrodes according to the first to third examples and the first comparative example
  • Fig. 4B illustrates the relationships among the peak counts Pc and the conductances.
  • a multiple regression line obtained by a multiple regression analysis is shown.
  • Fig. 5 illustrates the relationship between the cut-off value ⁇ c and a coefficient of determination R 2 obtained by a multiple regression analysis.
  • square plots represent the relationship between the conductance and the arithmetic mean roughness Ra
  • circular plots represent the relationship between the conductance and the peak count Pc.
  • the arithmetic mean roughness Ra and the peak count Pc of the fine irregular surface of the titanium that has not yet undergone platinization and blasting correlate with the conductance of the platinized electrode.
  • the metal plate for an electrode and the electrode formed of this metal plate for an electrode can be preferably used in an apparatus such as an electrolysis apparatus used to perform electrolysis in an aqueous solution or an organic solvent.
EP14002711.1A 2013-09-18 2014-08-01 Metallplatte für Elektrode sowie Elektrode Withdrawn EP2851453A1 (de)

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JP2013193463A JP6234754B2 (ja) 2013-09-18 2013-09-18 電極用金属板及び電極

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Cited By (1)

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WO2016208863A1 (ko) 2015-06-24 2016-12-29 엘에스엠트론 주식회사 전해 동박, 그 전해 동박을 포함하는 집전체, 그 집전체를 포함하는 전극, 그 전극을 포함하는 이차전지 및 이의 제조방법

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KR102472146B1 (ko) * 2018-03-28 2022-11-28 주식회사 엘지화학 전해용 전극의 제조방법 및 이를 사용하여 제조된 전해용 전극

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EP0407349A2 (de) * 1989-06-30 1991-01-09 Eltech Systems Corporation Elektrode für elektrolytische Verfahren und Verfahren zur Herstellung der Elektrode
EP0576402A1 (de) * 1992-06-25 1993-12-29 Eltech Systems Corporation Elektrode mit verbesserter Lebensdauer
JPH08109490A (ja) * 1994-08-16 1996-04-30 Daiso Co Ltd 酸素発生用陽極の製法
WO1997017478A1 (de) * 1995-11-08 1997-05-15 Fissler Gmbh Verfahren zur erzeugung einer antihaftbeschichtung sowie mit einer solchen versehene gegenstände
JPH11350162A (ja) * 1998-06-04 1999-12-21 Kobe Steel Ltd セメントとの密着性に優れた金属板
JP3467954B2 (ja) 1996-02-29 2003-11-17 Ｊｆｅスチール株式会社 金属帯の連続電気めっき方法
JP2005029834A (ja) * 2003-07-11 2005-02-03 Sumitomo Titanium Corp 不溶性陽極用チタン基体及びその製造方法
US20100084266A1 (en) * 2007-04-18 2010-04-08 Industrie De Nora S.P.A. Electrodes with Mechanically Roughened Surface for Electrochemical Applications

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US5324407A (en) * 1989-06-30 1994-06-28 Eltech Systems Corporation Substrate of improved plasma sprayed surface morphology and its use as an electrode in an electrolytic cell
TW197475B (de) * 1990-12-26 1993-01-01 Eltech Systems Corp
IT1317969B1 (it) * 2000-06-09 2003-07-21 Nora Elettrodi De Elettrodo caratterizzato da elevata adesione di uno strato cataliticosuperficiale.
ITMI20070980A1 (it) * 2007-05-15 2008-11-16 Industrie De Nora Spa Elettrodo per celle elettrolitiche a membrana
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Publication number Priority date Publication date Assignee Title
EP0407349A2 (de) * 1989-06-30 1991-01-09 Eltech Systems Corporation Elektrode für elektrolytische Verfahren und Verfahren zur Herstellung der Elektrode
EP0576402A1 (de) * 1992-06-25 1993-12-29 Eltech Systems Corporation Elektrode mit verbesserter Lebensdauer
JPH08109490A (ja) * 1994-08-16 1996-04-30 Daiso Co Ltd 酸素発生用陽極の製法
WO1997017478A1 (de) * 1995-11-08 1997-05-15 Fissler Gmbh Verfahren zur erzeugung einer antihaftbeschichtung sowie mit einer solchen versehene gegenstände
JP3467954B2 (ja) 1996-02-29 2003-11-17 Ｊｆｅスチール株式会社 金属帯の連続電気めっき方法
JPH11350162A (ja) * 1998-06-04 1999-12-21 Kobe Steel Ltd セメントとの密着性に優れた金属板
JP2005029834A (ja) * 2003-07-11 2005-02-03 Sumitomo Titanium Corp 不溶性陽極用チタン基体及びその製造方法
US20100084266A1 (en) * 2007-04-18 2010-04-08 Industrie De Nora S.P.A. Electrodes with Mechanically Roughened Surface for Electrochemical Applications

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016208863A1 (ko) 2015-06-24 2016-12-29 엘에스엠트론 주식회사 전해 동박, 그 전해 동박을 포함하는 집전체, 그 집전체를 포함하는 전극, 그 전극을 포함하는 이차전지 및 이의 제조방법

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JP6234754B2 (ja) 2017-11-22
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