CN105734654A - Anode preparation method - Google Patents
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- CN105734654A CN105734654A CN201410754769.2A CN201410754769A CN105734654A CN 105734654 A CN105734654 A CN 105734654A CN 201410754769 A CN201410754769 A CN 201410754769A CN 105734654 A CN105734654 A CN 105734654A
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Abstract
The invention discloses an anode preparation method. The anode preparation method comprises the following steps that valve-shaped metal is used as a substrate, a crack-free valve-shaped metal bottom layer and a crack-free composite precious metal surface layer are sequentially formed on the substrate after acid etching, and a crack-free anode is prepared. The invention further discloses application of the anode prepared through the anode preparation method in electroplating, wet metallurgy and tinsel preparation. The crack-free valve-shaped metal bottom layer and the crack-free composite precious metal surface layer with specific organic solvent are adopted by the anode provided by the invention, the service life of the anode is effectively prolonged, and the anode has the following advantages that the bath voltage of the anode is decreased by 0.05 V to 0.3 V compared with existing titanium-based metallic oxide anodes and the service life is more than two times longer than that of the existing titanium-based metallic oxide anodes when the anode is applied to electroplating, wet metallurgy and tinsel preparation.
Description
Technical field
The invention belongs to anode preparation method field, particularly relate to a kind of preparation method without be full of cracks structure dimensional stable anode.
Background technology
Plating, hydrometallurgy or metal forming are prepared etc. in electrolysis and are required that anode material has higher corrosion resistance and service life.In plating, hydrometallurgy or metal forming preparation, a large amount of insoluble anodes adopted are graphite, pb-ag alloy or titanium matrix metal oxide anode at present.Graphite mechanical strength is low, corrosion resistance is poor, and easily causes carbon content rising in cathodic deposition metallic product；Although pb-ag alloy has higher electric conductivity, low fusing point, good processing characteristics and mechanical strength, but slight dissolving still occurs in electrolytic process；Ti-support metal oxide anode is serious owing to chapping in thermal decomposition process, understands fast-falling and cause anodic passivity in use procedure.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide without be full of cracks, performance remarkable, long service life, it is adaptable to plating, hydrometallurgy or metal forming such as prepare at the anode preparation method without be full of cracks in field.
For achieving the above object, present invention employs following technical scheme:
A kind of anode preparation method, comprises the steps: with valve metal for matrix, after acid etching, forms the valve-type metal back layer without be full of cracks and the composite noble metal surface layer without be full of cracks successively, can be prepared by without be full of cracks anode on matrix.
As the further optimization of such scheme, described matrix is netted or tabular.
Further, described acid etching comprises the steps: to be placed on matrix in one or more mixed liquors by a certain percentage of hydrochloric acid, sulphuric acid or oxalic acid, then adding thermal etching a period of time, further, described matrix etches 1～30 hour under 60～120 degree.
Further, the described forming process without be full of cracks valve-type metal back layer includes: by matrix after acid etching, valve-type metal salt solution is coated in the surface of described matrix, then heat drying, reheat and decompose, naturally cool to room temperature, according to above step repetitive coatings, dry and decompose for several times, preparing the valve-type metal back layer without be full of cracks；Further, after matrix acid etching, valve-type metal salt solution is coated in the surface of described matrix, dry 10～30 minutes at 100 DEG C～150 DEG C, decompose 30 to 120 minutes at 450 DEG C～550 DEG C, naturally cool to room temperature, according to above step, repetitive coatings, dry and decompose 1～10 time, prepare the valve-type metal back layer without be full of cracks, wherein said valve-type metal salt solution composed as follows: ethanol tantalum 0.1%～2.0%(w/v), butter of tin 0%～20%(w/v), butyl titanate 0%～5.0%(w/v), organic solvent 80～90% (v/v), hydrochloric acid 0%～10%(w/v), organic solution is with methanol, ethanol, one or more of propanol or n-butyl alcohol mix by a certain percentage；Preferably, organic solution includes: methanol 0～10% (v/v), ethanol 10～50% (v/v), isopropanol 10～60% (v/v), n-butyl alcohol 20～80% (v/v)；Further, described organic solution includes: methanol 0～5% (v/v), ethanol 20～30% (v/v), isopropanol 20～40% (v/v), n-butyl alcohol 60～70% (v/v).
Further, described valve metal includes titanium, zirconium or tantalum, it is more preferred to, described valve metal is titanium.
Further, the described forming process without be full of cracks composite noble metal surface layer includes: composite noble metal saline solution is coated in the surface of the anode substrate of the netted or tabular without be full of cracks valve-type metal back layer being initially formed, then heat drying, reheat and decompose, naturally cool to room temperature, according to above step repetitive coatings, dry and decompose for several times, preparing the noble metal top layer without be full of cracks；nullFurther，Composite noble metal saline solution is coated in the surface of the anode substrate of the netted or tabular without be full of cracks valve-type metal back layer being initially formed，Dry 10～30 minutes at 100 DEG C～150 DEG C，Decompose 30 to 120 minutes at 450 DEG C～550 DEG C，Naturally cool to room temperature，According to above step，Repetitive coatings、Dry and decompose 30～60 times，Prepare the noble metal top layer without be full of cracks，Wherein said composite noble metal saline solution composed as follows: chloro-iridic acid 0.2～5.0% (v/v)，Ethanol tantalum 0%～2.0%(w/v)、Organic solvent 80%～95% (v/v)、Stabilizer 0%～20%(w/v)，Described organic solvent is that organic solution is with methanol、Ethanol、One or more of propanol or n-butyl alcohol mix by a certain percentage，Described stabilizer is hydrochloric acid、One or more of nitric acid or hydrogen peroxide mix by a certain percentage；It is highly preferred that described organic solution includes: methanol 0～10% (v/v), ethanol 10～50% (v/v), isopropanol 10～60% (v/v), n-butyl alcohol 20～80% (v/v)；Further, described organic solution includes: methanol 0～5% (v/v), ethanol 20～30% (v/v), isopropanol 20～40% (v/v), n-butyl alcohol 60～70% (v/v)；Further, described stabilizer includes: hydrochloric acid 1～30% (v/v), nitric acid 0～10% (v/v), hydrogen peroxide 60～90% (v/v)；Most preferably, described organic solution includes: hydrochloric acid 5～15% (v/v), nitric acid 0～3% (v/v), hydrogen peroxide 85～90% (v/v).
Further, described valve-type metal back layer thickness is 0.2～2.0 micron.
Further, the thickness on described metal composite oxide top layer is 5～8mm.
The invention still further relates to above-mentioned anode preparation method prepared anode purposes in plating, hydrometallurgy and metal forming preparation.
Beneficial effects of the present invention main manifestations is: anode prepared by the present invention adopts the valve-type metal back layer without be full of cracks prepared of specific organic solvent and without the composite noble metal top layer chapped, effectively extend electrode life, use it in plating, hydrometallurgy and metal forming preparation and have the advantage that tank voltage is than existing Ti-support metal oxide anode decline 0.05V～0.3V；Exceed existing Ti-support metal oxide anode length more than 2 times service life.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is further described, but the present invention should not be limited only to these embodiments.
Embodiment 1
A kind of preparation method without be full of cracks structure dimensional stable anode, it comprises the steps:
1. pretreatment: put into by the titanium net of 15cm2 in the aqueous sulfuric acid of 20wt%, takes out after etching 2h, clean surface with deionized water in micro-situation of boiling；
2. formed without be full of cracks valve-type metal back layer: valve-type metallic solution is coated on titanium surface, dry 15 minutes at 120 DEG C, decompose 2 hours at 480 DEG C, naturally cool to room temperature, according to above step, repetitive coatings, dry and decompose 6 times, surface must be arrived and be formed with the titanium net of the valve-type metal back layer without be full of cracks, wherein the component of precious metal solution includes as follows: ethanol tantalum 1.5%(w/v), butter of tin 10%(w/v), butyl titanate 0.1%(w/v), ethanol 15% (v/v), isopropanol 15% (v/v), n-butyl alcohol 60% (v/v), hydrochloric acid 3%(w/v)；
3. formed without be full of cracks composite noble metal top layer: surface step 2. obtained is formed without after be full of cracks valve-type metal back layer titanium net cooling, composite noble metal saline solution is coated in the surface of described matrix, dry 30 minutes at 150 DEG C, decompose 2 hours at 550 DEG C, naturally cool to room temperature, according to above step, repetitive coatings, dry and decompose 40 times, prepare the noble metal top layer without be full of cracks, the composition of wherein said composite noble metal saline solution includes as follows: chloro-iridic acid 1.0% (v/v), ethanol tantalum 0.45%(w/v), ethanol 15% (v/v), isopropanol 15% (v/v), n-butyl alcohol 60% (v/v), hydrogen peroxide 8%(w/v).
Embodiment 2
A kind of preparation method without be full of cracks structure dimensional stable anode, it comprises the steps:
1. pretreatment: put into by the titanium net of 15cm2 in the oxalic acid aqueous solution of 10wt%, takes out after etching 8 (h), clean surface with deionized water in micro-situation of boiling；
2. formed without be full of cracks valve-type metal back layer: valve-type metallic solution is coated on titanium surface, dry 15 minutes at 120 DEG C, decompose 2 hours at 480 DEG C, naturally cool to room temperature, according to above step, repetitive coatings, dry and decompose 6 times, surface must be arrived and be formed with the titanium net of the valve-type metal back layer without be full of cracks, wherein the composition of precious metal solution includes as follows: ethanol tantalum 1.5%(w/v), butter of tin 10%(w/v), butyl titanate 0.1%(w/v), ethanol 20%, isopropanol 15% (v/v), n-butyl alcohol 55% (v/v), hydrochloric acid 3%(w/v)；
3. formed without be full of cracks composite noble metal top layer: surface step 2. obtained is formed without after be full of cracks valve-type metal back layer titanium net cooling, composite noble metal saline solution is coated in the surface of described matrix, dry 30 minutes at 150 DEG C, decompose 2 hours at 550 DEG C, naturally cool to room temperature, according to above step, repetitive coatings, dry and decompose 40 times, prepare the noble metal top layer without be full of cracks, the composition of wherein said composite noble metal saline solution includes as follows: chloro-iridic acid 1.0% (v/v), ethanol tantalum 0.45%(w/v), ethanol 20% (v/v), isopropanol 15% (v/v), n-butyl alcohol 60% (v/v), hydrogen peroxide 3%(w/v).
Comparative example 1
The preparation method of a kind of Ti-support metal oxide anode, it comprises the steps:
1. pretreatment: put into by the titanium net of 15cm2 in the aqueous sulfuric acid of 20wt%, takes out after etching 2h, clean surface with deionized water in micro-situation of boiling；
2. valve-type metal back layer is formed: valve-type metallic solution is coated on titanium surface, dry 15 minutes at 120 DEG C, decompose 2 hours at 480 DEG C, naturally cool to room temperature, according to above step, repetitive coatings, dry and decompose 6 times, must arrive surface and be formed with the titanium net without the valve-type metal back layer chapped, wherein the composition of precious metal solution includes as follows: ethanol tantalum 1.5%(w/v), isopropanol 45% (v/v), n-butyl alcohol 50% (v/v), hydrochloric acid 3.5%(w/v)；
3. composite noble metal top layer is formed: after surface step 2. obtained is formed with the cooling of valve-type metal back layer titanium net, composite noble metal saline solution is coated in the surface of described matrix, dry 30 minutes at 150 DEG C, decompose 2 hours at 550 DEG C, naturally cool to room temperature, according to above step, repetitive coatings, dry and decompose 20 times, prepare noble metal top layer, the composition of wherein said composite noble metal saline solution includes as follows: chloro-iridic acid 2.0% (v/v), ethanol tantalum 0.9%(w/v), isopropanol 38% (v/v), n-butyl alcohol 60% (v/v).
Anode above-described embodiment 1,2 and comparative example 1 prepared is at 15% sulphuric acid, temperature 50 degree, electric current density 60000A/M2Environment under carry out reinforcing life test, as shown in table 1, there it can be seen that embodiment 1 and 2 without be full of cracks structure dimensional stable anode corrosion rate be substantially reduced relative to comparative example, reinforcing life significantly improves.
Table 1 reinforcing life contrasts
| Tank voltage (V) | Reinforcing life (H) | |
| Embodiment 1 | 5.20 | 2506 |
| Embodiment 2 | 5.25 | 2550 |
| Comparative example 1 | 5.50 | 1201 |
Above-described embodiment is only for illustrating technology design and the feature of the present invention; its object is to allow person skilled in the art will appreciate that present disclosure and to implement according to this; can not limit the scope of the invention with this; all equivalences made according to spirit of the invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (9)
1. an anode preparation method, it is characterised in that comprise the steps: with valve metal for matrix, after acid etching, forms the valve-type metal back layer without be full of cracks and the composite noble metal surface layer without be full of cracks successively on matrix, can be prepared by without be full of cracks anode.
2. anode preparation method according to claim 1, it is characterised in that described matrix is netted or tabular.
3. anode preparation method according to claim 1, it is characterised in that described acid etching comprises the steps: to be placed on by matrix in one or more mixed liquors by a certain percentage of hydrochloric acid, sulphuric acid or oxalic acid, then adds thermal etching a period of time.
4. anode preparation method according to claim 1, it is characterized in that, the described forming process without be full of cracks valve-type metal back layer includes: by matrix after acid etching, valve-type metal salt solution is coated in the surface of described matrix, then heat drying, reheats and decomposes, naturally cool to room temperature, according to above step repetitive coatings, dry and decompose for several times, preparing the valve-type metal back layer without be full of cracks.
5. anode preparation method according to claim 1, it is characterised in that described valve metal includes titanium, zirconium or tantalum.
6. anode preparation method according to claim 2, it is characterized in that, the described forming process without be full of cracks composite noble metal surface layer includes: composite noble metal saline solution is coated in the surface of the anode substrate of the netted or tabular without be full of cracks valve-type metal back layer being initially formed, then heat drying, reheat and decompose, naturally cool to room temperature, according to above step repetitive coatings, dry and decompose for several times, preparing the noble metal top layer without be full of cracks.
7. anode preparation method according to claim 1, it is characterised in that described valve-type metal back layer thickness is 0.2～2.0 micron.
8. the anode preparation method according to claim 1 or 7, it is characterised in that the thickness on described metal composite oxide top layer is 5～8mm.
9. the anode that the arbitrary described anode preparation method of claim 1～7 prepares purposes in plating, hydrometallurgy and metal forming preparation.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106119899A (en) * | 2016-06-28 | 2016-11-16 | 苏州吉岛电极科技有限公司 | Waste water recycling insoluble anode plate preparation method |
| CN106676618A (en) * | 2017-03-22 | 2017-05-17 | 苏州市汉宜化学有限公司 | Improved gun-color electroplating meshed anode |
| CN107413762A (en) * | 2017-09-06 | 2017-12-01 | 沈阳中科腐蚀控制工程技术有限公司 | A kind of nuclear facilities ultrasonic electrochemical radioactive pollution decontamination plant and method |
| CN109868464A (en) * | 2019-03-11 | 2019-06-11 | 江阴安诺电极有限公司 | Anode plate with noble coatings |
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| CN107413762A (en) * | 2017-09-06 | 2017-12-01 | 沈阳中科腐蚀控制工程技术有限公司 | A kind of nuclear facilities ultrasonic electrochemical radioactive pollution decontamination plant and method |
| CN109868464A (en) * | 2019-03-11 | 2019-06-11 | 江阴安诺电极有限公司 | Anode plate with noble coatings |
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