CN103492616A - Coating for metallic cell-element materials of an electrolytic cell - Google Patents
Coating for metallic cell-element materials of an electrolytic cell Download PDFInfo
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- CN103492616A CN103492616A CN201180063955.6A CN201180063955A CN103492616A CN 103492616 A CN103492616 A CN 103492616A CN 201180063955 A CN201180063955 A CN 201180063955A CN 103492616 A CN103492616 A CN 103492616A
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- 239000000463 material Substances 0.000 title claims abstract description 9
- 239000011248 coating agent Substances 0.000 title claims description 18
- 238000000576 coating method Methods 0.000 title claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 35
- 229910052709 silver Inorganic materials 0.000 claims abstract description 28
- 239000004332 silver Substances 0.000 claims abstract description 28
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims description 35
- 229910052760 oxygen Inorganic materials 0.000 claims description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 33
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002926 oxygen Chemical class 0.000 claims description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 abstract 4
- 229910001923 silver oxide Inorganic materials 0.000 abstract 2
- -1 Ni-sulphide Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000012799 electrically-conductive coating Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 22
- 238000005260 corrosion Methods 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
- 229910052737 gold Inorganic materials 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 4
- 229920003935 Flemion® Polymers 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000036039 immunity Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018502 Ni—H Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
-
- 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
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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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
- 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
-
- 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
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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)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention relates to a cathode half-shell of an electrolytic cell, comprising metallic cell-element components, comprising DEG a metallic support structure (2) welded to the rear wall of the cathode half shell (1), and at least one metallic spring element (4) arranged thereon in a plane-parallel manner, DEG an oxygen-consuming cathode arranged on the at least one metallic spring element and comprising a perforated metallic carrier (5) and a catalyst strip (6), mechanically pressed thereonto, consisting of PTFE and silver oxide, the silver oxide being reduced in the electrolysis operation to obtain silver and therefore producing a uniform connection, characterised in that it is highly conductive, between the components of the oxygen-consuming cathode and the at least one spring element, at least one of the metallic components being provided with an electrically conductive coating comprising at least two layers, DEG one first layer, which is applied directly to the cell-element materials, being selected from a group which contains Au, B-doped nickel, Ni-sulphide, and mixtures thereof, this first layer having a layer thickness of between 0.005 and 0.2 [mu]m, and DEG a second layer, applied to the first layer, consisting of silver and having a layer thickness of between 0.1 to 30 [mu]m.
Description
The present invention relates to a kind of negative electrode half housing, wherein these metal assemblies have and take the particular conductivity coating that the preamble of claim 1 is feature.
In electrochemical process, chemical reaction is controlled by foreign current.In electrochemical cell, need conduction, stable, cheap conductor to carry out transmission electronic.At this, nickel has been proved to be a kind of desirable electrode materials.But shortcoming is when electrode is worked in the potential range of nickel oxide or the formation of nickel hydroxide species, forms bad or nonconducting nickel surface.Due to these low potential levels, the formation of oxide compound or oxyhydroxide occurs in many processes.
Damaged the efficiency of whole system in the ohmic loss of nickel surface, for example zinc/air and nickle/metal hydrides battery, the oxygen cathode in chloric alkali electrolysis or the oxygen electrode in alkaline fuel cell.
When pure nickel as electrolysis analyse oxygen electrode the time, these bad or nonconducting oxide compounds or hydroxide layer are hindering property.Even but insulation layer also has negative impact in following system: wherein as conductive mesh, expanded metal or sheet material, nickel and catalytic active substance be as carbon, the contacts such as Platinised plated Carbon.For example, oxide compound or hydroxide layer hinder best electric current, even use oxygen depletion electrode (Sauerstoffverzehrelektroden), therefore need some measures with improvement or maintain the electroconductibility in industrial electrolysis.
In document, in " the electrochemical equilibrium atlas (1974) in the aqueous solution " of Marcel Pourbaix, recording many charts about electrochemical stability.The result of Pourbaix shows, pH condition and cathode potential 13 to 15 are measured with respect to NHE higher than about 0.4-0.6V() under, use in the chloric alkali electrolysis process of oxygen depletion negative electrode under electrical load, the formation of the known nickel oxide in form of passivation has occurred.
The startup of chlor-alkali electrolysis cell and close another problem caused and be, when the middle equipotential (measuring with respect to NHE) of about 0.6V by the time, solubility oxyhydroxide forms.Because Pourbaix figure can't make relevant dynamic (dynamical) statement, because decomposition reaction (i.e. corrosion) causes the actual formation of unpredictable these oxyhydroxide.Therefore, need actual electrolysis test so that under oxidizing condition, as in the situation that use the chloric alkali electrolysis of oxygen depletion negative electrode to determine the behavior of nickel.
Various patent specifications, for example EP1033419B1 or EP1092789A1 have described the electrolyzer of the chloric alkali electrolysis for using the oxygen depletion negative electrode, and wherein nickel is used as the material of the metal assembly of cathode side.The corrosion stability that there is no the nickel of the compound formation form of explanation in non-conductive oxide compound or oxyhydroxide.
EP1041176A1 has described a kind of method of using the electrolyzer of gas diffusion electrode, in order to minimize, is fed to the ohmic loss of oxygen depletion negative electrode (referred to here as gas diffusion electrode) process at electric current by the metal assembly for distribution of current.It has comprised having good electroconductibility and being embodied as the description of the coating of metal.Do not provide particularly the further details about its corrosion stability.
DE102004034886A1 has described a kind of method for the production of the electric conductive oxidation nickel surface.Here, the bad electroconductibility of nickel oxide surfaces by under the existence of hydrogen peroxide under cold condition subsequently the chemical doping with alkalimetal oxide significantly improve.Therefore this application is specially adapted to the working conditions at fuel cell, store battery and chloric alkali electrolysis.
At first the method for describing in DE102004034886A1 is successfully used to use the work of the laboratory chlor-alkali electrolysis cell of oxygen depletion.Oxygen depletion negative electrode (it for example is manufactured in EP1402587B1 or DE3710168A1 and is described) is used to this.These electrodes comprise conductive carrier, nickel wire net normally, the catalyzer band that on it, rolling silver/PTFE or silver suboxide/PTFE mixture are made.The carrier of gas diffusion electrode and nickel distributing switch electrically contact, and according to the method for describing in DE102004034886A1, its electroconductibility is improved.In the working process in these ponds, laboratory; the signs of corrosion of the form that the rising of voltage do not detected or decompose with nickel; although this pond is closed repeatedly, therefore can suppose that DE102004034886A1 has described a kind of effective ways of avoiding corrosion for the protection of nickel.
EP1601817A1 described a kind of business development and for the electrolyzer of traditional chloric alkali electrolysis.US7670472B2 has described a kind of electrolyzer that is illustrated in the design configurations of cathode compartment, and it allows electrolyzer for carry out the chloric alkali electrolysis of work by the oxygen depletion negative electrode.
In the design of the electrolyzer described in EP1601817A1, on the basis at the technical characterictic of US7670472B2, changed, so that the electrolyzer that allows gained is for by the chloric alkali electrolysis of oxygen depletion work.For this, a kind of electrode formed by the nickel carrier, the catalyzer band that on this nickel carrier, rolling has silver suboxide and PTFE to make, as roughly described in DE3710168A1, be used as the oxygen depletion negative electrode.The electric current supply that is arranged in the oxygen depletion negative electrode of cathode compartment is realized by this way: the sheet type supporting structure that is parallel to the rear wall placement of negative electrode inserts, and described structure is electrically connected to this rear wall via the contact pin of vertically arranging by welding joint.An elastic element is attached to this supporting structure, with negative electrode half housing in this pond of box lunch, with together with anodic semi-shell is screwed in the time, creates pressure with the carrier web of oxygen depletion negative electrode and is connected, thereby guarantee to electrically contact and uniform distribution of current.This elastic element is described to some extent in various patent specifications, for example, at EP1446515A2, particularly in EP1451389A2, and comprises the thread various compressible stratums of metal, and these layers are guaranteed elasticity in sandwich coarctate mode.
The method for the treatment of nickel oxide surfaces of describing in DE102004034886A1 is used in the nickel component, with the electroconductibility of the nickel oxide surfaces guaranteeing in the course of the work to be produced by passivation.
In test series 1, (use Flemion F8020 barrier film, active electrolytic surface is 2.7m to the electrolyzer of two such redesigns
2) in current density, be 4kA/m
2, working temperature is 88 ° of C, and the NaCl anode solution concentration is 210g/l, and NaOH catholyte emission concentration is 32%w/w, uses the saturated moistening oxygen work of stoichiometry excessive 20%.
fig. 1show the voltage curve at front 65 days two electrolyzers of work.Each electrolyzer is used different symbol (hypographous rhombus and unblanketed trilateral).
In first 30 days of work, electrolyzer shows stable cell voltage.In the 30th day of work, the electric current of these two electrolyzers is closed.After restarting, reach 4kA/m
2current density, the form that these two kinds of electrolyzers all increase with the voltage of 100mV has at the most shown the ohmic resistance increased.Through the work of 4 days, electrolyzer was closed again again.After restarting, reach 4kA/m
2current density, ohmic resistance further increases, and causes the extra voltage of about 200mV to increase.Work other approximately after 30 days, close two electrolyzers, check assembly.This shows, the assembly that nickel is made, supporting structure and elastic element, electroconductibility greatly reduce.Check the oxygen depletion negative electrode used in the pond, laboratory, and compare with reference sample.In laboratory work, this assembly is compared the voltage that reference sample also shows increase, and this may reduce owing to the electroconductibility that makes the nickel carrier web due to oxidation at least partly.The provide protection of the process of describing in DE102004034886A1, therefore invalid under certain electrical potential and working conditions, when this obviously occurs in electrolyzer and is closed.
Thermodynamic(al)equilibrium reaction based on precious metals such as silver and gold, in " the electrochemical equilibrium atlas (1974) in the aqueous solution ", describe, electrochemical stability figure for the chloric alkali electrolysis working conditions under 85 ° of C is recalculated, to obtain the detailed overview of electrochemical conditions:
For nickel, for 10
-6mol/kg, 85 ° of relative NHE(standard hydrogen electrodes of C) result, with the form (stability diagram) of simplifying, be shown in
fig. 2.Here, regional A is characterised in that passivation, and regional B and C are characterised in that corrosion, and regional D is characterised in that immunity
according to this situation, form the corrosion area of oxyhydroxide at 85 ° of C, in starting zone (load and electromotive force increase) and closing closed region (load and electromotive force reduce), all pass, so these have represented harsh working conditions.
For gold, for 10
-6mol/kg, 85 ° of relative NHE(standard hydrogen electrodes of C) result, with the form (stability diagram) of simplifying, be shown in
fig. 3.Here, regional A is characterised in that passivation, and regional B is characterised in that corrosion, and regional D is characterised in that immunity.
Be similar to the nickel shown in Fig. 2, the figure shows one have in iso-electric possible corrosion area, wherein can form oxyhydroxide.Yet, in alkaline alkali lye, use the gold test almost not show any decomposition sign.Therefore, the conclusion that can draw is to exist kinetics to intercept, and for the chloric alkali electrolysis under oxidizing condition, gold can be regarded as stable metal.
For silver, for 10
-6mol/kg, 85 ° of relative NHE(standard hydrogen electrodes of C) result, with the form (stability diagram) of simplifying, be shown in
fig. 4.Here, regional A is characterised in that passivation, and regional B is characterised in that corrosion, and regional D is characterised in that immunity.
From
fig. 4clearly, although in the acid pH scope, silver also has narrow corrosion area.In alkalescence, particularly the silver under oxidizing condition is tending towards the passivation by forming oxide species.Therefore will provide corrosion stability, in the conductivity problems had under the chloric alkali electrolysis condition of oxygen depletion negative electrode, needs be tested.
WO01/57290A1 " electrolyzer with gas diffusion electrode " has described an electrolyzer with gas diffusion electrode, and what arouse attention is the defencive function of silver coating under oxidizing condition.Particularly, it has described a metallic conductor with perforate, and described conductor is made by silver, stainless steel or nickel, although nickel should preferably be coated with silver.
Document and numerous workers' experience confirms the stability of silver on nickel, and the nickel component of electrolyzer is electrosilvering.For this reason, apply the approximately coating of 10 μ m of thickness to nickel.
At 2, two electrolyzers of test series, with the method non-stop run of similar test series 1, tested.These two unit all have 2.7m
2active electrolytic surface and be equipped with Flemion F8020 barrier film.Uninterrupted current density is 4kA/m
2, working temperature is 88 ° of C, and the NaCl anode solution concentration is 210g/l, and NaOH catholyte emission concentration is 32%w/w, uses the saturated moistening oxygen work of stoichiometry excessive 20%.
fig. 5show the voltage curve that work surpasses 80 days.Each electrolyzer is used different symbol (hypographous rhombus and unblanketed trilateral).
According to
fig. 5the result of test series 2 shows that voltage increases again.Be this time continuous.Repeatedly started during operation and closed step, cell voltage is not had not to obviously impact, unlike based on
fig. 1the observations to test series 1.
Work and check the electrolyzer elastic element after 80 days, analyze the situation of metal support structure and metallic elastic component.By way of example, the cross section Photomicrograph of the silver-plated nickel single line of this elastic element is presented in Fig. 6 with the ratio of 100:1.Photomicrograph is clearly shown that from the peeling off of the single line sample of bottom, and demonstrates loosening silver coating and approximately 50% minimizing of coat-thickness from the sample at top.
Material contrast between the upper and lower sample of electrolyzer element also shows the transfer of the silver of decomposition, and this silver dissolves on top because of corrosion, in the bottom of electrolyzer, again deposits (not shown data).This shows, under the oxidization electrolysis condition, the nickel that simply is electroplate with one deck silver must not meet the connection of electrochemical stability.
These tests show, further need to provide coating, with the connection of the electrochemical stability of the constant electroconductibility form that obtains the metal assembly in negative electrode half housing, and above-mentioned shortcoming do not occur.
Therefore, the objective of the invention is to realize following target:
-a kind of alternative anti-corrosion protection coating of metal pool component element of negative electrode half housing of electrolyzer is provided
-guarantee that the bond strength of the lip-deep coating of pond component element increases, in order to can not form non-conductive oxide skin
The steady operation of-electrolyzer, no matter the startup of arbitrary number of times and closing, under given current loading within the longer time constant as far as possible cell voltage, thereby longer life cycle is arranged
-be minimized in the ohmic loss during electric current conducts to oxygen depletion negative electrode metallic carrier from metal assembly, thus the minimum conduction loss
This purpose is that a kind of negative electrode half housing of the electrolyzer by comprising the metal pool component element is realized, this negative electrode half housing comprises
-be welded to a metal support structure of the rear wall of negative electrode half housing, and plane run-in index (planparallel) arrangement at least one metallic elastic component thereon,
-mono-oxygen depletion negative electrode, be arranged on this at least one metallic elastic component, described oxygen depletion negative electrode comprises the mechanically pressure fitted catalyzer band of being made by PTFE and silver suboxide thereon of the metallic carrier of a perforation and, wherein said silver suboxide is reduced into silver in the electrolysis working process, and now between the assembly of this oxygen depletion negative electrode and described at least one elastic element, generate the connection of homogeneous, described connection be take high conductivity as feature
Wherein at least one metal assembly is provided with a conductive coating that comprises at least two layers, wherein
-mono-the first layer, be applied directly to the pond element material and be, is to be selected from the group of the sulfide of the nickel that comprises Au, B doping, Ni and their mixture, and the layer thickness of this first layer is 0.005 to 0.2 μ m, and
-mono-second layer, be applied on the first layer and be made from silver, and the layer thickness of this second layer is 0.1 to 30 μ m.
The present invention also proposes claim, and all ponds component element that comprise in this negative electrode half housing and conduction current is all coated.Here, preferably those pond component elements that contact with alkali lye of negative electrode half housing of electrolyzer have coating of the present invention.
Claim is also proposed, the purposes of negative electrode half housing of the present invention in the electrolyzer of chloric alkali electrolysis.
Below figure be used for describing in more detail the present invention.
Fig. 1: the electrolytic cell voltage of test series 1: shown in be the voltage curve of first 65 days of electrolyzer work, this electrolyzer is used the electrode described in DE102004034886A1.
Fig. 2: Ni-H
2o is at the stability diagram of the simplification of 85 ° of relative NHE of C
Fig. 3: Au-H
2o is at the stability diagram of the simplification of 85 ° of relative NHE of C
Fig. 4: Ag-H
2o is at the stability diagram of the simplification of 85 ° of relative NHE of C
Fig. 5: the electrolytic cell voltage of test series 2: shown in be that the work of electrolyzer surpasses the voltage curve of 80 days, this electrolyzer is used the pond component element of the metal with the thick silver layer of 10 μ m.
Fig. 6: from the cross section Photomicrograph of the 100:1 ratio of the silver-plated nickel wire of test series 2
Fig. 7: the electrolytic cell voltage of test series 3: shown in be that the work of electrolyzer surpasses the voltage curve of 240 days, this electrolyzer is used the pond component element of the metal that is coated with thin gold layer that 0.15 μ m is thick and the thick thick silver layer of 25 μ m.
Fig. 8: from the cross section Photomicrograph of the 25:1 ratio of the silver-plated nickel wire with au intermediate layer of test series 3
Fig. 9: from the cross section Photomicrograph of the 500:1 ratio of the silver-plated nickel wire with au intermediate layer of test series 3
Figure 10: the SEM image with Ni-Ag key coat of light color gold layer
Figure 11: there is the pond component element of metal of coating of the present invention in the basic arrangement of negative electrode half housing.
Known from materials chemistry, nickel and silver do not engage.Even more than fusing point, these metals still can not mix, and they just form a monotectic system.Due to this behavior and be not suitable for nickel/Jin Hejin/silver-colored mixture, started the coating test of 3 layer systems.Consequently, the gold layer of the nickel component 0.15 μ m that first coated one deck is thin, the then silver layer of one deck 25 μ m.The nickel component of preparation is arranged in the chlor-alkali electrolysis cell of the coming of new with oxygen depletion negative electrode thus, and carries out the continuous duty test in test series 3.
In test series 3, with the similar mode of test series 2, to move continuously two electrolyzers of test.These two ponds all have 2.7m
2active electrolytic surface and be equipped with Flemion F8020 barrier film.Uninterrupted current density is 4kA/m
2, working temperature is 88 ° of C, and the NaCl anode solution concentration is 210g/l, and NaOH catholyte emission concentration is 32%w/w, uses the saturated moistening oxygen work of stoichiometry excessive 20%.
fig. 7 show test series 3 work and surpass the voltage curve of 240 days.Each electrolyzer is used different symbol (hypographous rhombus and unblanketed trilateral).
According to
fig. 7the result of test series 3, showing voltage slight when starting increases, this can be summed up as the characteristic of the oxygen depletion negative electrode of use.Follow and surpass the steady stage more than 200 days by work.Repeatedly start and close not obviously impact of electrolytic cell voltage.
After having tested, to 3 metal assemblies, supporting structure, elastic element and comprise the oxygen depletion negative electrode of carrier web, checked and carried out the confirmation situation by Photomicrograph.This illustrates at Fig. 8 and Fig. 9.Do not observe the significantly loosening of layer or peel off.Nickel supporting structure uniformly-coating silver, surface is slightly coarse.
Surprisingly, during checking also find to be arranged in the physically combination uniformly between the elastic element under it between oxygen depletion negative electrode and plane run-in index.The silver suboxide that is rolled into the catalyzer band of oxygen depletion negative electrode is reduced into silver when starting electrolyzer for the first time.In this process, the metallic carrier of oxygen depletion negative electrode and at least one elastic element with coating of the present invention, obtain physically combination extremely uniformly from the silver bar band, because the silver layer of assembly has formed Chemical bond at least in part, described being combined in while disassembling is difficult to become flexible.Such combination makes at electric current has low ohmic loss during by electrolyzer, and reaches and can repeatedly do not started during long term operation and close the low and stable cell voltage affected.
figure 10show the situation of the middle gold layer of the key coat formed between nickel and silver.Not significantly corrosion is also arranged here.
Finally,
figure 11show the basic arrangement of the metal pool component element with coating of the present invention.Base portion is negative electrode half shell (1).The metal contact pin (2) that is soldered to rear wall and distributing switch (3) assembly is arranged to be parallel to narrow sidewall.Elastic element (4) component pressure is matched with between distributing switch (3) and oxygen depletion negative electrode.The oxygen depletion negative electrode that the plane parallel formula arranges therewith is comprised of the metallic carrier of a perforation or carrier web (5) and rolling catalyzer band (6) thereon, wherein, in process at electrolyzer for the work of expection purpose, metallic carrier (5) and elastic element (4) form and are connected, described connection take high conductivity and so low ohmic resistance be feature.
Claims (4)
1. wrap negative electrode half housing of the electrolyzer of metallic pond component element, comprise
O is welded to a metal support structure of the rear wall of this negative electrode half housing, and run-in index ground, plane arrangement at least one metallic elastic component thereon,
Oxygen depletion negative electrode of o, this oxygen depletion negative electrode is arranged on this at least one metallic elastic component, wherein said oxygen depletion negative electrode comprises the mechanically pressure fitted catalyzer band of being made by PTFE and silver suboxide thereon of the metallic carrier of a perforation and, wherein said silver suboxide is reduced into silver in the electrolysis working process, and now between the assembly of oxygen depletion negative electrode and described at least one elastic element, generate being connected of homogeneous, described connection be take high conductivity as feature
Wherein at least one metal assembly is provided with the conductive coating that comprises at least two layers, wherein
The first layer of ■, this first layer is applied directly on the element material of pond, is to be selected from the nickel that comprises Au, B doping, and in the group of the sulfide of Ni and their mixture, wherein the layer thickness of this first layer is 0.005 to 0.2 μ m, and
Second layer of ■, this second layer is applied on the first layer and is made from silver, and wherein the layer thickness of this second layer is 0.1 to 30 μ m.
2. negative electrode half housing of electrolyzer according to claim 1, is characterized in that, the pond component element of all conduction current of this electrolyzer is all coated.
3. negative electrode half housing of electrolyzer according to claim 1 and 2, is characterized in that, the pond component element that all and alkali lye of this electrolyzer contacts is all coated.
4. according to the purposes of negative electrode half housing of the described electrolyzer of any one of the preceding claims, it is characterized in that, this electrolyzer is for chloric alkali electrolysis.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011008163A DE102011008163A1 (en) | 2011-01-10 | 2011-01-10 | Coating for metallic cell element materials of an electrolytic cell |
| DE102011008163.1 | 2011-01-10 | ||
| PCT/EP2011/005965 WO2012095126A1 (en) | 2011-01-10 | 2011-11-29 | Coating for metallic cell-element materials of an electrolytic cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103492616A true CN103492616A (en) | 2014-01-01 |
Family
ID=45217479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180063955.6A Pending CN103492616A (en) | 2011-01-10 | 2011-11-29 | Coating for metallic cell-element materials of an electrolytic cell |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP2663669B1 (en) |
| JP (1) | JP2014505793A (en) |
| KR (1) | KR20140034138A (en) |
| CN (1) | CN103492616A (en) |
| CA (1) | CA2824173A1 (en) |
| DE (1) | DE102011008163A1 (en) |
| RU (1) | RU2573558C2 (en) |
| WO (1) | WO2012095126A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103981533A (en) * | 2014-05-30 | 2014-08-13 | 李欣 | Cathode fastening spring bearer plate structure of electrolysis ozonator |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2012095126A1 (en) | 2012-07-19 |
| EP2663669A1 (en) | 2013-11-20 |
| CA2824173A1 (en) | 2012-07-19 |
| DE102011008163A1 (en) | 2012-07-12 |
| RU2573558C2 (en) | 2016-01-20 |
| JP2014505793A (en) | 2014-03-06 |
| RU2013134646A (en) | 2015-02-20 |
| KR20140034138A (en) | 2014-03-19 |
| EP2663669B1 (en) | 2015-04-29 |
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