CN102062754A - Preparation method of cobalt oxide gas-diffusion electrode - Google Patents
Preparation method of cobalt oxide gas-diffusion electrode Download PDFInfo
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- CN102062754A CN102062754A CN2009102380786A CN200910238078A CN102062754A CN 102062754 A CN102062754 A CN 102062754A CN 2009102380786 A CN2009102380786 A CN 2009102380786A CN 200910238078 A CN200910238078 A CN 200910238078A CN 102062754 A CN102062754 A CN 102062754A
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Abstract
The invention discloses a preparation method of a cobalt oxide catalyst gas-diffusion electrode, relating to a gas-diffusion electrode technology. The preparation method uses cobalt oxide as a catalyst and comprises the following steps: A) sputtering a metal material on the surface of a hydrophobic gas-permeable porous polymer thin film to prepare an inert electrode layer; B) depositing a metal cobalt layer on the surface of the inert electrode by using a sputtering method; and C) oxidizing the metal cobalt layer into a required cobalt oxide layer by using an anodic oxidation method so as to obtain the finished product, cobalt oxide electrode having uniform high catalytic activity. For the prepared cobalt oxide gas-diffusion electrode, the catalyst is uniformly distributed and has stable performance and high activity.
Description
Technical field
The present invention relates to the gas-diffusion electrode technical field, particularly relating to a kind of is the preparation method of the gas-diffusion electrode of catalyzer with the cobalt oxide.
Background technology
Gas-diffusion electrode is that a kind of gas that can allow freely passes through, the extraordinary electrode that can stop electrolytic solution to ooze out simultaneously, and it is mainly used in electrochemical appliances such as preparation gas sensor, gas sensing electrode, fuel cell, gas battery, electrolytic tank.
The gas-diffusion electrode that present document relates to generally adopts metal electrode, as: platinum, palladium, gold, rhodium, ruthenium, iridium, silver, copper, nickel, and their alloy etc.These metal materials are conductive material, also usually are the catalyzer of electrochemical reaction simultaneously.Use the situation of compound catalyst less in the gas-diffusion electrode, this mainly is because majority of compounds material electric conductivity does not reach the level of metal, even insulation fully, so electrochemical reaction can not continue to carry out on this material, or can not carry out at a high speed.But some galvanochemistry chemical reaction must use some distinctive catalyst systems, and the catalyzer that uses when this catalyst system and catalyzing is the relatively poor material of electric conductivity, or during insulating material, such catalysis electrode is difficult for preparation.
Cobalt oxide is a kind of important oxide catalyst, can be used as electrocatalysis oxidation reaction, the nitrate radical of ammonia, alcohol, aldehyde, the electrical catalyze reduction catalyst for reaction of solubility carbonyl containing compound in galvanochemistry.But owing to there is not enough electric conductivity, electrode must mix with the conductive material of other inertia.Even now, the catalytic efficiency of electrode are still very low, can not satisfy the basic demand of heavy-current discharge, and for example: the ammonia concentration scope that can accept with the electrochemical device of this material preparation is very little, usually only in volume fraction 0-500 * 10
-6About, cobalt oxide is a kind of semiconductor material, and electric conductivity is bad, has only in the contacted narrow range in cobalt oxide and inert electrode surface, and electrochemical reaction could be carried out smoothly, and efficient is very low.
For addressing this problem, patent EP1600768A1 uses in electrochemical reaction cell and contains divalent cobalt ion (Co
2+) electrolytic solution of salt solusion replaces directly use metal oxide electrode, catalytic efficiency increases, but there is following problem in this method: at first, relevant electrochemical reaction system must allow to use cobalt ions, secondly, it is neutral and acid that such electrochemical reactor must keep, otherwise the precipitation of hydroxide reaction of cobalt will take place.When such electrode contacts with ammonia, if the concentration of ammonia is higher, as volume fraction 0.01, perhaps electrode contacts for a long time with ammonia, cobalt ions contacts with ammonia, and precipitation reaction will take place, the precipitation of hydroxide of cobalt destroys the ionic equilibrium in the electrochemical pond simultaneously with the micropore of barrier gas diffusion electrode, and the electrochemical device performance is descended.
Patent US5344546 utilizes electrochemical deposition method with the oxidate of the cobalt surface to inert electrode, and performance is more stable.This method has improved the useful area of cobalt oxide electrode within the specific limits, and still, this method prepares the cobalt oxide electrode and has following several problems:
At first, be difficult to prepare the catalysis electrode of uniformity, this is because of the electrochemical deposition cobalt oxide, and oxide always at first begins deposition from some position of electrode surface, just spread to other position gradually after depositing to certain thickness, this makes total some position of electrode surface not deposit cobalt oxide; And the thickness of other position cobalt oxides is very high, the duct on the barrier gas diffusion electrode, and cobalt oxide comes off part when serious.Electrode surface is inhomogeneous will to cause subsidiary reaction to take place, and produce the signal noise of electrode.
Secondly, the extremely difficult control of deposition reaction is in acid and neutral electrolyte, above-mentioned deposition reaction does not take place, and above-mentioned deposition reaction only just takes place, along with the generation of deposition reaction under subalkaline condition, alkali lye must constantly be replenished, to keep suitable pH value in electrolytic solution; The adding of alkali lye is wayward, and one is excessive slightly, will generate precipitation of hydroxide.
Summary of the invention
The objective of the invention is: provide a kind of preparation method of cobalt oxide gas-diffusion electrode, the cobalt oxide gas-diffusion electrode of this method preparation, its cobalt oxide layer uniformity, and efficient height.
For achieving the above object, technical solution of the present invention is:
A kind of preparation method of cobalt oxide gas-diffusion electrode is a catalyzer with the cobalt oxide; It is:
A) the porous polymer film surface sputtering metal material at hydrophobic, air-permeability prepares one deck inert electrode;
B) utilize sputtering method deposition preparation layer of metal cobalt again on the surface of inert electrode;
C) with anodizing layer of metal cobalt is oxidized to needed cobalt oxide layer again, promptly obtains finished product: cobalt oxide electrode with even high catalytic activity.
The porous polymer film of the hydrophobic, air-permeability described preparation method, its described steps A) by the macromolecular material preparation, has the porous membrane in space, and the surface keeps hydrophobic property; Hole on the macromolecular material runs through film, and gas can be diffused into the opposite side of film from a side of film; The lip-deep metal material of porous polymer film that sputters at hydrophobic, air-permeability is distributed on the skeleton structure of polymeric material, makes electrode keep porous structure.
Described preparation method, its described macromolecular material, be teflon, polychlorotrifluoroethylene, polyvinylidene fluoride, polypropylene, tygon, Polyvinylchloride, polystyrene, polysulfones, polyethersulfone, silicon rubber, EP rubbers or ethylene-propylene copolymer one of them.
Described preparation method, the metal material of its described inert electrode is one of them a tool chemical inertness conductive material of platinum, gold, palladium, ruthenium, iridium, osmium, graphite, vitreous carbon, tungsten, tungsten carbon composite, silit or molybdenum carbide.
Described preparation method, its described step B) in, the preparation of layer of metal cobalt be with the sputter simultaneously of the metal material of inert electrode or alternating sputtering to the inert material surface, layer of metal cobalt forms certain concentration gradients, from the inert electrode surface, content is more and more higher, and finally forms certain thickness pure cobalt part, and making has a transition bed between inert electrode layer and the layer of metal cobalt.
Described preparation method, its described step C) in, the anodic oxidation reactions of metallic cobalt carries out in neutral electrolyte or alkalescent electrolytic solution, oxidation voltage 1～120V, and electric current is not less than 0.4A, and the retention time is≤2 hours behind the 120V; Electrolyte be potassium nitrate, potassium chloride, sodium nitrate, sodium chloride, sodium sulphate, ammonium nitrate, ammonium chloride, ammonium sulfate, sal tartari, sodium carbonate, potassium oxalate or sodium oxalate one of them.
Described preparation method, the porous polymer film of its described hydrophobic, air-permeability, thickness should guarantee in the sputter procedure, inert electrode material and metallic cobalt material can not be penetrated into the opposite side of film, its thickness is between 0.02mm～2.0mm, voidage is between 10%～85%, and average pore size is between 0.3～50um; The thickness of while inert electrode layer, the gas permeation speed of assurance entire electrode material, the thickness of its inert metal layer is about 300nm.
Described preparation method, its described step C) after, also comprise step D) ageing: ageing was used after 5～10 days, or kept using after 4～6 hours under the 120V voltage in the anodic oxidation pond.
Advantage of the present invention is:
In the electrode of the present invention's preparation, cobalt oxide catalyst is evenly distributed, and does not have tangible visible spot, does not have the catalyzer obscission, the electrode surface uniformity.
When the cobalt oxide gas-diffusion electrode is used for the catalytic oxidation of ammonia, area 1cm
2The electrode discharge electric current in 1mA, linear with the concentration of ammonia.This value is higher 9.5 times than electrochemical deposition cobalt oxide electrode, and cobalt oxide powder directly painting method is high 15～20 times than using.
The electrode of the present invention's preparation, high conformity, with the electrode discharge electric current and the ammonia concentration relationship basically identical of batch preparation, wherein volume fraction 1000 * 10
-6The ammonia average 200uA that on electrode, discharges, different electrodes subtract deviation and are not more than ± 2.0%, this deviation of electrode of different batches preparation is not more than ± 5.0%, consistance is better.
Description of drawings
Fig. 1 is preparation method's FB(flow block) of a kind of cobalt oxide gas-diffusion electrode of the present invention;
Fig. 2 is the PTFE porous membrane of the cobalt oxide/platinum electrode of the inventive method preparation;
Fig. 3 is the cyclic voltammetric analysis of ammonia oxidation reaction on the cobalt oxide electrode.
Embodiment
The main points of the inventive method are: sputter inert electrode on hydrophobic porous polymer film, and then at the transition bed of inert electrode surface sputtering inert electrode material and metallic cobalt, the content of cobalt increases gradually in the transition bed, until forming pure cobalt layer.Then, utilize anodizing that cobalt oxidation is become cobalt oxide.The purpose of doing like this is to make the cobalt oxide uniformity, and the efficient height.
Sputter one deck inert metal material on hydrophobic porous polymer film, this layer inert metal can be platinum, gold, palladium, rhodium, ruthenium, iridium, also can be the material such as material with carbon element, silit, tungsten carbide of inertia.Wherein hydrophobic porous polymer film can be teflon, polychlorotrifluoroethylene, polyvinylidene fluoride, polypropylene, tygon, Polyvinylchloride, polystyrene, polysulfones, polyethersulfone, silicon rubber, EP rubbers, ethylene propylene copolymer etc., the thickness of thin polymer film is between 0.02mm～2.0mm, voidage is between 10%～85%, and average pore size is between about 0.3～50um.About the about 300nm of the thickness of inert metal layer.
Between transition region thickness 100～500nm, the content of cobalt is to increase progressively along the direction perpendicular to film in the transition bed, until reaching simple metal cobalt layer.Between the about 100～500nm of the thickness of layer of metal cobalt.The gross thickness of inert metal layer, transition bed, layer of metal cobalt is not more than 50% of porous polymer film average pore size, to avoid blocked up metal level to cover the hole of hydrophobic polymer porous membrane fully, as shown in Figure 2, after the deposit metallic material, the voidage of whole film should keep about 20%～80% of former voidage.
With above-mentioned electrode is anode, in neutral electrolyte or alkaline electrolyte metallic cobalt is oxidized to cobalt oxide.Oxidation voltage changes from 1V to 120V, and electric current is not less than 0.4A.When can being considered as oxidation reaction during greater than 120V, finishes voltage.
Electrode is immersed in the potassium nitrate solution of 1M, ageing can be used after about 5～10 days.If do not allow digestion time long, then should in the anodic oxidation pond, keep under the 120V voltage 4～6 hours, so that remaining cobalt metal exhaustive oxidation.
Fig. 3 is the volt-ampere characteristic of ammonia oxidation on the cobalt oxide electrode that makes, and as can be seen from Figure 2, can observe the catalytic oxidation electric current of a tangible ammonia more than 0.28V.
Shown in Figure 1, the preparation method's FB(flow block) for a kind of cobalt oxide gas-diffusion electrode of the present invention comprises following concrete steps:
(1) deposit metallic material on the hydrophobic polymer film
With needed porous polymer film, after cleaning oil removing, with the inactive, conductive material about one side sputter 300nm, these materials comprise: platinum, gold, palladium, rhodium, ruthenium, iridium also can be carbon, silit, tungsten carbide etc.
While sputter inert material and metallic cobalt form the transition bed that cobalt content increases progressively on the sputtering unit of two targets, and transition region thickness is between 100～500nm.After the transition bed preparation finishes, simple metal cobalt layer between the simple about 100～500nm of sputter thickness.
(2) anodic oxidation of metallic cobalt
With above-mentioned freshly prepd electrode is anode, in neutral or alkaline electrolytic solution, electrolyte comprises: potassium nitrate, potassium chloride, sodium nitrate, sodium chloride, sodium sulphate, sal tartari, sodium carbonate etc., and contain a certain amount of ammonium ion in the electrolytic solution or contain certain amount of ammonia water.Oxidation voltage changes from 1V to 120V, and electric current is not less than 0.4A.When can being considered as oxidation reaction during greater than 120V, finishes voltage.
Embodiment 1
Thickness is porous Teflon (PTFE) film of 0.5mm, voidage 46%, average pore size 1.0um cleans film 2 hours in acetone, cyclohexane respectively, in 0.5M KOH solution, clean after 1 hour, in deionized water, clean to alkali free metal ion repeatedly.
Side at the PTFE film prepares the thick platinum of 200nm, makes platinum target and cobalt target build-up of luminance simultaneously in the dual-target sputtering platform, reduces the platinum target build-up of luminance time gradually, after this transition bed reaches 200nm, stops the platinum target, and the sputter cobalt is until 300nm separately.
In the 1.0M potassium nitrate solution, with above-mentioned new system power backup anode very, be negative electrode with the platinum electrode, the oxidation voltage that raises gradually makes electric current keep 400mA, rises to about 120V until voltage.After 120V keeps 2 hours, stop electrochemical reaction.
Electrode is immersed in the 1.0M potassium nitrate solution stores.
Embodiment 2:
In embodiment 1, after the sputter platinum layer, alternating sputtering platinum and cobalt increase the sputtering time of cobalt gradually, and the sputtering time that reduces platinum reaches about 200nm until transition bed, stops sputter platinum, continuously sputter cobalt 200nm.
In the Klorvess Liquid of 1.2M neutrality, under 25 ℃, will be negative electrode with the carbon electrode with above-mentioned new system power backup anode very, the oxidation voltage that raises gradually makes electric current keep 400mA, rises to about 120V until voltage.After 120V keeps 2 hours, stop electrochemical reaction.
Embodiment 3:
Thickness is porous polyvinylidene chloride (PVDF) film of 0.3mm, voidage 60%, and average pore size 0.54um cleans film 2 hours in acetone, cyclohexane, deionized water respectively.
Side at the PVDF film prepares the thick ruthenium of 200nm, makes ruthenium target and cobalt target replace build-up of luminance in the dual-target sputtering platform, reduces the ruthenium target build-up of luminance time gradually, after this transition bed reaches 200nm, stops the platinum target, and the sputter cobalt is until 200nm separately.
In the 1.0M sodium carbonate liquor, with above-mentioned new system power backup anode very, be negative electrode with the platinum electrode, the oxidation voltage that raises gradually makes electric current keep 400mA, rises to about 120V until voltage.After 120V keeps 2 hours, stop electrochemical reaction.
Embodiment 4:
Thickness is porous ethylene-propylene copolymer (PPE) film of 0.2mm, voidage 50%, and average pore size 0.45um cleans film 2 hours in acetone, cyclohexane, deionized water respectively.
Side at the PVDF film prepares the thick iridium of 200nm, makes iridium target and cobalt target replace build-up of luminance in the dual-target sputtering platform, reduces the ruthenium target build-up of luminance time gradually, after this transition bed reaches 200nm, stops the platinum target, and the sputter cobalt is until 200nm separately.
Claims (8)
1. the preparation method of a cobalt oxide gas-diffusion electrode is a catalyzer with the cobalt oxide; It is characterized in that:
A) the porous polymer film surface sputtering metal material at hydrophobic, air-permeability prepares one deck inert electrode;
B) utilize sputtering method deposition preparation layer of metal cobalt again on the surface of inert electrode;
C) with anodizing layer of metal cobalt is oxidized to needed cobalt oxide layer again, promptly obtains finished product: cobalt oxide electrode with even high catalytic activity.
2. preparation method according to claim 1 is characterized in that: the porous polymer film of the hydrophobic, air-permeability described steps A), by the macromolecular material preparation, have the porous membrane in space, and the surface keeps hydrophobic property; Hole on the macromolecular material runs through film, and gas can be diffused into the opposite side of film from a side of film; The lip-deep metal material of porous polymer film that sputters at hydrophobic, air-permeability is distributed on the skeleton structure of polymeric material, makes electrode keep porous structure.
3. preparation method according to claim 2, it is characterized in that: described macromolecular material, for teflon, polychlorotrifluoroethylene, polyvinylidene fluoride, polypropylene, tygon, Polyvinylchloride, polystyrene, polysulfones, polyethersulfone, silicon rubber, EP rubbers or ethylene-propylene copolymer one of them.
4. preparation method according to claim 1 and 2 is characterized in that: the metal material of described inert electrode is one of them a tool chemical inertness conductive material of platinum, gold, palladium, ruthenium, iridium, osmium, graphite, vitreous carbon, tungsten, tungsten carbon composite, silit or molybdenum carbide.
5. according to claim 1 or 4 described preparation methods, it is characterized in that: described step B), the preparation of layer of metal cobalt be with the sputter simultaneously of the metal material of inert electrode or alternating sputtering to the inert material surface, layer of metal cobalt forms certain concentration gradients, from the inert electrode surface, content is more and more higher, and finally forms certain thickness pure cobalt part, and making has a transition bed between inert electrode layer and the layer of metal cobalt.
6. preparation method according to claim 1, it is characterized in that: described step C), the anodic oxidation reactions of metallic cobalt carries out in neutral electrolyte or alkalescent electrolytic solution, oxidation voltage 1～120V, electric current is not less than 0.4A, and the retention time is≤2 hours behind the 120V; Electrolyte be potassium nitrate, potassium chloride, sodium nitrate, sodium chloride, sodium sulphate, ammonium nitrate, ammonium chloride, ammonium sulfate, sal tartari, sodium carbonate, potassium oxalate or sodium oxalate one of them.
7. preparation method according to claim 1, it is characterized in that: the porous polymer film of described hydrophobic, air-permeability, its thickness should guarantee in the sputter procedure, inert electrode material and metallic cobalt material can not be penetrated into the opposite side of film, its thickness is between 0.02mm～2.0mm, voidage is between 10%～85%, and average pore size is between 0.3～50um; The thickness of while inert electrode layer, the gas permeation speed of assurance entire electrode material, the thickness of its inert metal layer is about 300nm.
8. preparation method according to claim 1 is characterized in that: described step C), also comprise step D) ageing: ageing was used after 5～10 days, or kept using after 4～6 hours under the 120V voltage in the anodic oxidation pond.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711424A (en) * | 2017-01-12 | 2017-05-24 | 青岛大学 | Cobaltous oxide based nano complex electrode material and preparation method thereof |
| CN106802339A (en) * | 2017-01-19 | 2017-06-06 | 烟台睿创微纳技术股份有限公司 | A kind of array type MEMS gas sensors |
| CN111229227A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Cobalt catalyst and preparation and application thereof |
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| US3671323A (en) * | 1970-01-12 | 1972-06-20 | Westinghouse Electric Corp | Hydrophobic layers for gas diffusion electrodes |
| CN1862856A (en) * | 2005-05-14 | 2006-11-15 | 鸿富锦精密工业（深圳）有限公司 | Gas diffusion electrode and mfg. method thereof |
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2009
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3671323A (en) * | 1970-01-12 | 1972-06-20 | Westinghouse Electric Corp | Hydrophobic layers for gas diffusion electrodes |
| CN1862856A (en) * | 2005-05-14 | 2006-11-15 | 鸿富锦精密工业（深圳）有限公司 | Gas diffusion electrode and mfg. method thereof |
Non-Patent Citations (1)
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| 董汉鹏等: "氧化钴催化薄膜的制备及在微量氨检测中的应用", 《现代化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711424A (en) * | 2017-01-12 | 2017-05-24 | 青岛大学 | Cobaltous oxide based nano complex electrode material and preparation method thereof |
| CN106711424B (en) * | 2017-01-12 | 2019-10-18 | 青岛大学 | A kind of cobalt protoxide base nano-complex electrode material and preparation method thereof |
| CN106802339A (en) * | 2017-01-19 | 2017-06-06 | 烟台睿创微纳技术股份有限公司 | A kind of array type MEMS gas sensors |
| CN111229227A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Cobalt catalyst and preparation and application thereof |
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Application publication date: 20110518 |