CN106011958B - A kind of cupromanganese plating solution and its application for being used to prepare copper galaxite coating - Google Patents
A kind of cupromanganese plating solution and its application for being used to prepare copper galaxite coating Download PDFInfo
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- CN106011958B CN106011958B CN201610643626.3A CN201610643626A CN106011958B CN 106011958 B CN106011958 B CN 106011958B CN 201610643626 A CN201610643626 A CN 201610643626A CN 106011958 B CN106011958 B CN 106011958B
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- cupromanganese
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
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- 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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
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- 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
- C25D5/48—After-treatment of electroplated surfaces
Abstract
It is used to prepare the cupromanganese plating solution of copper galaxite coating the invention provides a kind of, includes each component of following concentration：Copper ion source 0.025mol/L~0.1mol/L；Manganese ion source 0.25mol/L~1.0mol/L；Chelating agent 0.03mol/L~0.1mol/L；Buffer 20g/L~200g/L；Stabilizer 10g/L~50g/L；Surplus is solvent.Present invention also offers a kind of method that copper galaxite coating is prepared using the plating solution, comprise the following steps：First, oil removing and activation；2nd, electroplate；3rd, post-process.Present invention process is simple, condition is controllable, coating even compact, it is good with metalwork matrix adhesiveness, suitable for being deposited on soild oxide metal connector surface, via copper galaxite coating can be changed into after oxidation processes, SOFC service life is improved.
Description
Technical field
The invention belongs to electrochemical technology field, and in particular to a kind of cupromanganese for being used to prepare copper galaxite coating
Plating solution and its application.
Background technology
SOFC is a kind of all solid state chemical generated device, and it is under high temperature by the chemistry of reactant
Electric energy can be directly translated into, is green energy resource, environmental pollution is small.But its high operating cost hinders it to promote the use of, wherein
Connector is the critical component of SOFC, and accounts for the 30%~70% of totle drilling cost, as long as so significantly dropping
The cost of low connector, so that it may substantially reduce the cost of SOFC.Recently, with solid oxide fuel electricity
The running temperature in pond is reduced to 600 DEG C~800 DEG C from 1000 DEG C, and this causes cheap ferrite stainless steel material to substitute tradition pottery
Ceramic material prepares connector and is possibly realized.But the oxidation product that ferritic stainless steel aoxidizes generation at relatively high temperatures can make to connect
Resistance of getting an electric shock increases, and the Cr volatilizations in stainless steel can cause " negative electrode poisons ", cause battery performance to decay.Solving at present should
The main method of problem is to apply conductive protection coating on stainless steel connector surface.Wherein, heat endurance is good, electrical conductivity is high,
The moderate copper galaxite coating of thermal coefficient of expansion turns into one of maximally effective protective coating in stainless steel connector surface, enjoys people
Pay close attention to.
The main preparation method of copper galaxite coating has at present：Electro-deposition, slurry coating, silk-screen printing, plasma spray
Painting and physical vapour deposition (PVD) etc..Wherein electro-deposition method is to deposit cupromanganese coating using electroplating technology in stainless steel surfaces,
Alloy layer is changed into the method for copper galaxite through high-temperature oxydation afterwards.This method cost is cheap, coating layer thickness is adjustable, adapts to
The advantages that complicated substrate shape.But in cupromanganese plating system, Cu2+/ Cu normal potential is 0.337VH, Mn2+/Mn
Normal potential be -1.18VH, both differ greatly at normal potential, and manganese be can from the aqueous solution electrodepositable metal Plays
The most negative metal of current potential, so plating cupromanganese difficulty is very big.G.Zangari et al. is had found in simple sulfate system
PH can electroplate Cu-Mn alloys when being 2.6~2.8 and 6.4~6.8 in stainless steel surfaces.When current density is relatively low (<100mA·
cm-2), coating is spongiform；Current density is in 150mAcm-2~400mAcm-2When, coating is crystal；Current density compared with
When big>400mA·cm-2When, coating is intended to amorphous.Wherein, the preferable coating amount containing Cu of quality is 2at.%~14at.%.
Mn in copper galaxite1.5Cu1.5O4Thermal coefficient of expansion and electrical conductivity meet connector coating needs, so copper galaxite apply
The molar content of copper cannot be below 30% in layer, otherwise be difficult to obtain the copper galaxite coating for meeting performance requirement, therefore need
Adding suitable complexing agent to further cupromanganese sedimentation potential, make in cupromanganese coating that manganese content is moderate, quality of coating is good,
So need to invent a kind of new cupromanganese electroplate liquid to meet this demand.
The content of the invention
The technical problems to be solved by the invention are to be directed to above-mentioned the deficiencies in the prior art, there is provided a kind of chemical property is steady
Fixed, non-volatile pernicious gas, the cupromanganese plating solution of medicine environmental sound used.The plating solution preparing process is simple, and cost is low
It is honest and clean；Copper molar content in the copper galaxite coating prepared using the plating solution is not less than 30%.
In order to solve the above technical problems, the technical solution adopted by the present invention is：One kind is used to prepare copper galaxite coating
Cupromanganese plating solution, it is characterised in that include each component of following concentration：
Copper ion source 0.025mol/L~0.1mol/L；
Manganese ion source 0.25mol/L~1.0mol/L；
Chelating agent 0.03mol/L~0.1mol/L；
Buffer 20g/L~200g/L；
Stabilizer 10g/L~50g/L；
Surplus is solvent.
Above-mentioned a kind of cupromanganese plating solution for being used to prepare copper galaxite coating, it is characterised in that including following dense
The each component of degree：
Copper ion source 0.05mol/L；
Manganese ion source 0.5mol/L；
Chelating agent 0.05mol/L；
Buffer 30g/L；
Stabilizer 20g/L；
Surplus is solvent.
A kind of above-mentioned cupromanganese plating solution for being used to prepare copper galaxite coating, it is characterised in that the copper ion
Source is copper chloride.
A kind of above-mentioned cupromanganese plating solution for being used to prepare copper galaxite coating, it is characterised in that the manganese ion
Source is protochloride manganese.
A kind of above-mentioned cupromanganese plating solution for being used to prepare copper galaxite coating, it is characterised in that the chelating agent
For disodium ethylene diamine tetraacetate.
A kind of above-mentioned cupromanganese plating solution for being used to prepare copper galaxite coating, it is characterised in that the buffer
For ammonium chloride or boric acid.
A kind of above-mentioned cupromanganese plating solution for being used to prepare copper galaxite coating, it is characterised in that the stabilizer
For ammonium bromide.
Above-mentioned a kind of cupromanganese plating solution for being used to prepare copper galaxite coating, it is characterised in that the solvent is
Deionized water.
Above-mentioned a kind of cupromanganese plating solution for being used to prepare copper galaxite coating, it is characterised in that the copper manganese closes
The pH value of golden plating solution is 3~7.
In addition, present invention also offers a kind of method for preparing copper galaxite coating using above-mentioned cupromanganese plating solution,
Characterized in that, this method comprises the following steps：
Step 1: treatment before plating, including oil removal treatment and activation process, detailed process are：
Step 101, oil removal treatment：Alkaline degreaser is heated to 80 DEG C, after plating metal part then is placed in into heating
30min is soaked in alkaline degreaser, cleans up and dries after taking-up；The alkaline degreaser includes each group of following concentration
Point：Tertiary sodium phosphate 30g/L~40g/L, sodium carbonate 40g/L~50g/L, sodium hydroxide 50g/L~60g/L, sodium metasilicate 5g/L~
6g/L, surplus are deionized water；
Step 102, activation process：Plating metal part after oil removal treatment in step 101 is placed in hydrochloric acid-nitric acid Compound-acid
60s is soaked in liquid, is subsequently placed in the dilute sulfuric acid that mass percent concentration is 10%~20% and soaks 60s, is cleaned after taking-up dry
Only；HCl mass percent concentration is 20%~30%, HNO in the compound acid solution of hydrochloric acid-nitric acid3Mass percent it is dense
Spend for 5%~10%；
Step 2: electroplating processes：Plating metal part after activation process in step 102 is placed in and is loaded with cupromanganese plating
In the coating bath of liquid, using plating metal part as negative electrode, using graphite cake as anode, in 20 DEG C~25 DEG C of bath temperature, current density is
200mA·cm-2~700mAcm-2Under conditions of electroplate 10min~30min, afterwards by after plating metalwork take out, spend
Ionized water is dried up after cleaning up, and cupromanganese coating is obtained on metalwork surface；
Step 3: post processing：The plating of cupromanganese described in step 2 is placed in tube furnace, first protected in argon gas atmosphere
Shield, temperature are dehydrogenation 2h under conditions of 800 DEG C, then by the cupromanganese coating after dehydrogenation in air atmosphere, temperature
Spend for oxidation processes 2h under conditions of 800 DEG C, copper galaxite coating is finally obtained on metalwork surface.
The present invention has advantages below compared with prior art：
1st, cupromanganese plating chemistry of the present invention is stable, non-volatile pernicious gas, medicine environmental sound used.
2nd, cupromanganese plating solution preparing process of the present invention is simple, and cost is cheap, the copper galaxite prepared using the plating solution
Copper molar content in coating is not less than 30%.
3rd, after the electroplated processing of cupromanganese plating solution of the present invention, copper galaxite coating, the coating and metalwork base are obtained
The adhesion property of body is excellent.
4th, present invention process is simple, condition is controllable, coating even compact, good with metalwork matrix adhesiveness, suitable for heavy
Product is on soild oxide metal connector surface, via can be changed into copper galaxite coating after oxidation processes.Copper galaxite
Coating can improve the antioxygenic property of metal connector, reduce its area specific resistance, improve SOFC and be on active service the longevity
Life.
The present invention is described in further detail with reference to the accompanying drawings and examples.
Brief description of the drawings
Fig. 1 is the surface SEM photograph of the cupromanganese coating prepared using the cupromanganese plating solution of the embodiment of the present invention 1.
Fig. 2 is the surface SEM photograph of the copper galaxite coating prepared using the cupromanganese plating solution of the embodiment of the present invention 1.
Fig. 3 is the section SEM photograph of the copper galaxite coating prepared using the cupromanganese plating solution of the embodiment of the present invention 1.
Embodiment
Embodiment 1
The present embodiment includes each component of following concentration for preparing the cupromanganese plating solution of copper galaxite coating：
Copper ion source 0.05mol/L；The copper ion source is copper chloride；
Manganese ion source 0.5mol/L；The manganese ion source is manganese chloride；
Chelating agent 0.05mol/L；The chelating agent is disodium ethylene diamine tetraacetate；
Buffer 30g/L；The buffer is ammonium chloride or boric acid；
Stabilizer 20g/L；The stabilizer is ammonium bromide；
Surplus is solvent；The solvent is deionized water；
The pH value of the cupromanganese plating solution is 5.
The preparation method of plating solution described in the present embodiment is：
Step 1: chelating agent is added in deionized water, after being well mixed, while stirring into the solution dissolved with chelating agent
Copper ion source is added, stirs, obtains solution A；
Step 2: manganese ion source is dissolved in deionized water, buffer and stabilizer are then sequentially added, after stirring
Obtain solution B；
Step 3: after solution A is stirred into 1h, it is well mixed with solution B, stirs 2h, is adjusted pH value with watery hydrochloric acid, finally add
Water is settled to 1L, obtains cupromanganese plating solution.
The method that the present embodiment prepares copper galaxite coating using above-mentioned cupromanganese plating solution comprises the following steps：
Step 1: treatment before plating, including oil removal treatment and activation process, detailed process are：
Step 101, oil removal treatment：Alkaline degreaser is heated to 80 DEG C, after plating metal part then is placed in into heating
30min is soaked in alkaline degreaser, cleans up and dries after taking-up；The alkaline degreaser includes each group of following concentration
Point：Tertiary sodium phosphate 35g/L, sodium carbonate 45g/L, sodium hydroxide 55g/L, sodium metasilicate 5.5g/L, surplus are deionized water；
Step 102, activation process：Plating metal part after oil removal treatment in step 101 is placed in hydrochloric acid-nitric acid Compound-acid
60s is soaked in liquid, is subsequently placed in the dilute sulfuric acid that mass percent concentration is 15% and soaks 60s, cleaned up after taking-up；It is described
The compound acid solution of hydrochloric acid-nitric acid adds water to be formulated by commercially available concentrated hydrochloric acid and commercially available concentrated nitric acid, HCl in the compound acid solution prepared
Mass percent concentration is 25%, HNO3Mass percent concentration be 8%；
Step 2: electroplating processes：Plating metal part after activation process in step 102 is placed in and is loaded with cupromanganese plating
In the coating bath of liquid, using plating metal part as negative electrode, using graphite cake as anode, in 22 DEG C of bath temperature, current density 500mA
cm-2Under conditions of electroplate 20min, afterwards by after plating metalwork take out, dried up after being cleaned up with deionized water, in metal
Part surface obtains cupromanganese coating；
Step 3: post processing：The plating of cupromanganese described in step 2 is placed in tube furnace, protected in argon gas atmosphere,
Temperature is dehydrogenation 2h under conditions of 800 DEG C, is then in air atmosphere, temperature by the cupromanganese coating after dehydrogenation
Oxidation processes 2h under conditions of 800 DEG C, copper galaxite coating is finally obtained on metalwork surface.
Fig. 1 is the surface SEM photograph of the cupromanganese coating prepared using the present embodiment cupromanganese plating solution.Can by Fig. 1
To see the coating even compact, quality is good.Fig. 2 is that the copper galaxite prepared using the present embodiment cupromanganese plating solution is applied
The surface SEM photograph of layer.Fig. 3 is that the section SEM of the copper galaxite coating prepared using the present embodiment cupromanganese plating solution is shone
Piece, wherein I layers are metallic matrix, and II layers are copper galaxite coating.Understand that cupromanganese coating is oxidized with reference to Fig. 2 and Fig. 3
Uniform one layer of Cu is formed on metalwork surface afterwards2MnO4Spinelle coating, its atomic percentage [Cu]/[Mn]=2, meets to set
Meter requires.
The present embodiment cupromanganese plating chemistry is stable, non-volatile pernicious gas, medicine environmental sound used.Plating
Liquid preparing process is simple, and cost is cheap, after the electroplated processing of cupromanganese plating solution, obtains copper galaxite coating,
The adhesion property of the coating and metalwork matrix is excellent, suitable for being deposited on soild oxide metal connector surface, via oxygen
It can be changed into copper galaxite coating after change processing.Copper galaxite coating can improve the antioxygenic property of metal connector, drop
Its low area specific resistance, improve SOFC service life.
Embodiment 2
The present embodiment includes each component of following concentration for preparing the cupromanganese plating solution of copper galaxite coating：
Copper ion source 0.075mol/L；The copper ion source is copper chloride；
Manganese ion source 0.8mol/L；The manganese ion source is manganese chloride；
Chelating agent 0.05mol/L；The chelating agent is disodium ethylene diamine tetraacetate；
Buffer 100g/L；The buffer is ammonium chloride or boric acid；
Stabilizer 40g/L；The stabilizer is ammonium bromide；
Surplus is solvent；The solvent is deionized water；
The pH value of the cupromanganese plating solution is 6.
The preparation method of plating solution described in the present embodiment is：
Step 1: chelating agent is added in deionized water, after being well mixed, while stirring into the solution dissolved with chelating agent
Copper ion source is added, stirs, obtains solution A；
Step 2: manganese ion source is dissolved in deionized water, buffer and stabilizer are then sequentially added, after stirring
Obtain solution B；
Step 3: after solution A is stirred into 1h, it is well mixed with solution B, stirs 2h, is adjusted pH value with weak aqua ammonia, finally add
Water is settled to 1L, obtains cupromanganese plating solution.
The method that the present embodiment prepares copper galaxite coating using above-mentioned cupromanganese plating solution comprises the following steps：
Step 1: treatment before plating, including oil removal treatment and activation process, detailed process are：
Step 101, oil removal treatment：Alkaline degreaser is heated to 80 DEG C, after plating metal part then is placed in into heating
30min is soaked in alkaline degreaser, cleans up and dries after taking-up；The alkaline degreaser includes each group of following concentration
Point：Tertiary sodium phosphate 32g/L, sodium carbonate 48g/L, sodium hydroxide 56g/L, sodium metasilicate 5.7g/L, surplus are deionized water；
Step 102, activation process：Plating metal part after oil removal treatment in step 101 is placed in hydrochloric acid-nitric acid Compound-acid
60s is soaked in liquid, is subsequently placed in the dilute sulfuric acid that mass percent concentration is 18% and soaks 60s, cleaned up after taking-up；It is described
The compound acid solution of hydrochloric acid-nitric acid adds water to be formulated by commercially available concentrated hydrochloric acid and commercially available concentrated nitric acid, HCl in the compound acid solution prepared
Mass percent concentration is 20%, HNO3Mass percent concentration be 8%；
Step 2: electroplating processes：Plating metal part after activation process in step 102 is placed in and is loaded with cupromanganese plating
In the coating bath of liquid, using plating metal part as negative electrode, using graphite cake as anode, in 24 DEG C of bath temperature, current density 250mA
cm-2Under conditions of electroplate 18min, afterwards by after plating metalwork take out, dried up after being cleaned up with deionized water, in metal
Part surface obtains cupromanganese coating；
Step 3: post processing：The plating of cupromanganese described in step 2 is placed in tube furnace, protected in argon gas atmosphere,
Temperature is dehydrogenation 2h under conditions of 800 DEG C, is then in air atmosphere, temperature by the cupromanganese coating after dehydrogenation
Oxidation processes 2h under conditions of 800 DEG C, copper galaxite coating is finally obtained on metalwork surface.
The present embodiment cupromanganese plating chemistry is stable, non-volatile pernicious gas, medicine environmental sound used.Plating
Liquid preparing process is simple, and cost is cheap, after the electroplated processing of cupromanganese plating solution, obtains copper galaxite coating,
The adhesion property of the coating and metalwork matrix is excellent, suitable for being deposited on soild oxide metal connector surface, via oxygen
It can be changed into copper galaxite coating after change processing.Copper galaxite coating can improve the antioxygenic property of metal connector, drop
Its low area specific resistance, improve SOFC service life.
Embodiment 3
The present embodiment includes each component of following concentration for preparing the cupromanganese plating solution of copper galaxite coating：
Copper ion source 0.025mol/L；The copper ion source is copper chloride；
Manganese ion source 1.0mol/L；The manganese ion source is manganese chloride；
Chelating agent 0.03mol/L；The chelating agent is disodium ethylene diamine tetraacetate；
Buffer 200g/L；The buffer is ammonium chloride or boric acid；
Stabilizer 10g/L；The stabilizer is ammonium bromide；
Surplus is solvent；The solvent is deionized water；
The pH value of the cupromanganese plating solution is 3.
The preparation method of plating solution described in the present embodiment is：
Step 1: chelating agent is added in deionized water, after being well mixed, while stirring into the solution dissolved with chelating agent
Copper ion source is added, stirs, obtains solution A；
Step 2: manganese ion source is dissolved in deionized water, buffer and stabilizer are then sequentially added, after stirring
Obtain solution B；
Step 3: after solution A is stirred into 1h, it is well mixed with solution B, stirs 2h, is adjusted pH value with watery hydrochloric acid, finally add
Water is settled to 1L, obtains cupromanganese plating solution.
The method that the present embodiment prepares copper galaxite coating using above-mentioned cupromanganese plating solution comprises the following steps：
Step 1: treatment before plating, including oil removal treatment and activation process, detailed process are：
Step 101, oil removal treatment：Alkaline degreaser is heated to 80 DEG C, after plating metal part then is placed in into heating
30min is soaked in alkaline degreaser, cleans up and dries after taking-up；The alkaline degreaser includes each group of following concentration
Point：Tertiary sodium phosphate 30g/L, sodium carbonate 50g/L, sodium hydroxide 50g/L, sodium metasilicate 6g/L, surplus are deionized water；
Step 102, activation process：Plating metal part after oil removal treatment in step 101 is placed in hydrochloric acid-nitric acid Compound-acid
60s is soaked in liquid, is subsequently placed in the dilute sulfuric acid that mass percent concentration is 10% and soaks 60s, cleaned up after taking-up；It is described
The compound acid solution of hydrochloric acid-nitric acid adds water to be formulated by commercially available concentrated hydrochloric acid and commercially available concentrated nitric acid, HCl in the compound acid solution prepared
Mass percent concentration is 30%, HNO3Mass percent concentration be 5%；
Step 2: electroplating processes：Plating metal part after activation process in step 102 is placed in and is loaded with cupromanganese plating
In the coating bath of liquid, using plating metal part as negative electrode, using graphite cake as anode, in 20 DEG C of bath temperature, current density 700mA
cm-2Under conditions of electroplate 30min, afterwards by after plating metalwork take out, dried up after being cleaned up with deionized water, in metal
Part surface obtains cupromanganese coating；
Step 3: post processing：The plating of cupromanganese described in step 2 is placed in tube furnace, protected in argon gas atmosphere,
Temperature is dehydrogenation 2h under conditions of 800 DEG C, is then in air atmosphere, temperature by the cupromanganese coating after dehydrogenation
Oxidation processes 2h under conditions of 800 DEG C, copper galaxite coating is finally obtained on metalwork surface.
The present embodiment cupromanganese plating chemistry is stable, non-volatile pernicious gas, medicine environmental sound used.Plating
Liquid preparing process is simple, and cost is cheap, after the electroplated processing of cupromanganese plating solution, obtains copper galaxite coating,
The adhesion property of the coating and metalwork matrix is excellent, suitable for being deposited on soild oxide metal connector surface, via oxygen
It can be changed into copper galaxite coating after change processing.Copper galaxite coating can improve the antioxygenic property of metal connector, drop
Its low area specific resistance, improve SOFC service life.
Embodiment 4
The present embodiment includes each component of following concentration for preparing the cupromanganese plating solution of copper galaxite coating：
Copper ion source 0.1mol/L；The copper ion source is copper chloride；
Manganese ion source 0.25mol/L；The manganese ion source is manganese chloride；
Chelating agent 0.1mol/L；The chelating agent is disodium ethylene diamine tetraacetate；
Buffer 20g/L；The buffer is ammonium chloride or boric acid；
Stabilizer 50g/L；The stabilizer is ammonium bromide；
Surplus is solvent；The solvent is deionized water；
The pH value of the cupromanganese plating solution is 7.
The preparation method of plating solution described in the present embodiment is：
Step 1: chelating agent is added in deionized water, after being well mixed, while stirring into the solution dissolved with chelating agent
Copper ion source is added, stirs, obtains solution A；
Step 2: manganese ion source is dissolved in deionized water, buffer and stabilizer are then sequentially added, after stirring
Obtain solution B；
Step 3: after solution A is stirred into 1h, it is well mixed with solution B, stirs 2h, is adjusted pH value with weak aqua ammonia, finally add
Water is settled to 1L, obtains cupromanganese plating solution.
The method that the present embodiment prepares copper galaxite coating using above-mentioned cupromanganese plating solution comprises the following steps：
Step 1: treatment before plating, including oil removal treatment and activation process, detailed process are：
Step 101, oil removal treatment：Alkaline degreaser is heated to 80 DEG C, after plating metal part then is placed in into heating
30min is soaked in alkaline degreaser, cleans up and dries after taking-up；The alkaline degreaser includes each group of following concentration
Point：Tertiary sodium phosphate 40g/L, sodium carbonate 40g/L, sodium hydroxide 60g/L, sodium metasilicate 5g/L, surplus are deionized water；
Step 102, activation process：Plating metal part after oil removal treatment in step 101 is placed in hydrochloric acid-nitric acid Compound-acid
60s is soaked in liquid, is subsequently placed in the dilute sulfuric acid that mass percent concentration is 20% and soaks 60s, cleaned up after taking-up；It is described
The compound acid solution of hydrochloric acid-nitric acid adds water to be formulated by commercially available concentrated hydrochloric acid and commercially available concentrated nitric acid, HCl in the compound acid solution prepared
Mass percent concentration is 20%, HNO3Mass percent concentration be 10%；
Step 2: electroplating processes：Plating metal part after activation process in step 102 is placed in and is loaded with cupromanganese plating
In the coating bath of liquid, using plating metal part as negative electrode, using graphite cake as anode, in 25 DEG C of bath temperature, current density 200mA
cm-2, voltage be 20V under conditions of electroplate 10min, afterwards by after plating metalwork take out, after being cleaned up with deionized water
Drying, cupromanganese coating is obtained on metalwork surface；
Step 3: post processing：The plating of cupromanganese described in step 2 is placed in tube furnace, protected in argon gas atmosphere,
Temperature is dehydrogenation 2h under conditions of 800 DEG C, is then in air atmosphere, temperature by the cupromanganese coating after dehydrogenation
Oxidation processes 2h under conditions of 800 DEG C, copper galaxite coating is finally obtained on metalwork surface.
The present embodiment cupromanganese plating chemistry is stable, non-volatile pernicious gas, medicine environmental sound used.Plating
Liquid preparing process is simple, and cost is cheap, after the electroplated processing of cupromanganese plating solution, obtains copper galaxite coating,
The adhesion property of the coating and metalwork matrix is excellent, suitable for being deposited on soild oxide metal connector surface, via oxygen
It can be changed into copper galaxite coating after change processing.Copper galaxite coating can improve the antioxygenic property of metal connector, drop
Its low area specific resistance, improve SOFC service life.
In addition, applicant of the present invention, in order to determine the optimum proportioning of cupromanganese electroplate liquid, spy has carried out substantial amounts of reality
Checking, dosage optimization is carried out to the basic components of exploitation, adjust main salt concentration in formula, pH value, current density successively and sink
It is the product time, specific as follows：Electroplated in experiment using the stainless steel substrate of size identical 430, electroplating temperature is 25℃,
NH4Br and NH4Cl addition is constant, respectively 20g/L and 30g/L.Using SEM and EDS to obtained copper galaxite coating
Pattern, Cross Section Morphology and composition are tested.Influence of the selection of bath composition and pH value to copper galaxite appearance of coat
Test result is as shown in table 1.
Influence of the selection of the bath composition of table 1 and pH value to copper galaxite appearance of coat
As shown in Table 1, contrast test 1#, 2#, 3# and 4# is understood, obtains the optimization knot of convenient copper galaxite coating
Fruit is 1#.By carrying out sem analysis to coating surface, the coating uniform is fine and close, and quality is good, is formed on metalwork surface
Uniform one layer of Cu2MnO4Spinelle coating, its atomic percentage [Cu]/[Mn]=2, meets design requirement, is SOFC connectors
The development of surface protection coating provides technical support.
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions.It is every according to invention skill
Any simple modification, change and equivalence change that art is substantially made to above example, still fall within technical solution of the present invention
Protection domain in.
Claims (8)
1. a kind of cupromanganese plating solution for being used to prepare copper galaxite coating, it is characterised in that include each group of following concentration
Point：
Copper ion source 0.025mol/L~0.1mol/L；
Manganese ion source 0.25mol/L~0.5mol/L；The manganese ion source is protochloride manganese；
Chelating agent 0.03mol/L~0.1mol/L；
Buffer 20g/L~200g/L；
Stabilizer 10g/L~50g/L；The stabilizer is ammonium bromide；
Surplus is solvent；
The method that copper galaxite coating is prepared using the cupromanganese plating solution is comprised the following steps：
Step 1: treatment before plating, including oil removal treatment and activation process, detailed process are：
Step 101, oil removal treatment：Alkaline degreaser is heated to 80 DEG C, the alkalescence that then plating metal part is placed in after heating
30min is soaked in degreaser, cleans up and dries after taking-up；The alkaline degreaser includes each component of following concentration：Phosphorus
Sour trisodium 30g/L~40g/L, sodium carbonate 40g/L~50g/L, sodium hydroxide 50g/L~60g/L, sodium metasilicate 5g/L~6g/L,
Surplus is deionized water；
Step 102, activation process：Plating metal part after oil removal treatment in step 101 is placed in the compound acid solution of hydrochloric acid-nitric acid
60s is soaked, is subsequently placed in the dilute sulfuric acid that mass percent concentration is 10%~20% and soaks 60s, cleaned up after taking-up；Institute
The mass percent concentration for stating HCl in the compound acid solution of hydrochloric acid-nitric acid is 20%~30%, HNO3Mass percent concentration be
5%~10%；
Step 2: electroplating processes：Plating metal part after activation process in step 102 is placed in and is loaded with cupromanganese plating solution
In coating bath, using the plating metal part after activation process as negative electrode, using graphite cake as anode, in 20 DEG C~25 DEG C of bath temperature, electricity
Current density is 200mAcm-2~700mAcm-2Under conditions of electroplate 10min~30min, afterwards by the metalwork after plating
Take out, dried up after being cleaned up with deionized water, cupromanganese coating is obtained on metalwork surface；
Step 3: post processing：The plating of cupromanganese described in step 2 is placed in tube furnace, first protected in argon gas atmosphere, temperature
Spend for dehydrogenation 2h under conditions of 800 DEG C, be then in air atmosphere, temperature by the cupromanganese coating after dehydrogenation
Oxidation processes 2h under conditions of 800 DEG C, copper galaxite coating is finally obtained on metalwork surface.
2. a kind of cupromanganese plating solution for being used to prepare cupromanganese spinelle coating according to claim 1, its feature
It is, includes each component of following concentration：
Copper ion source 0.05mol/L；
Manganese ion source 0.5mol/L；
Chelating agent 0.05mol/L；
Buffer 30g/L；
Stabilizer 20g/L；
Surplus is solvent.
3. a kind of cupromanganese plating solution for being used to prepare copper galaxite coating according to claim 1 or 2, its feature exist
In the copper ion source is copper chloride.
4. a kind of cupromanganese plating solution for being used to prepare copper galaxite coating according to claim 1 or 2, its feature exist
In the chelating agent is disodium ethylene diamine tetraacetate.
5. a kind of cupromanganese plating solution for being used to prepare copper galaxite coating according to claim 1 or 2, its feature exist
In the buffer is ammonium chloride or boric acid.
6. a kind of cupromanganese plating solution for being used to prepare copper galaxite coating according to claim 1 or 2, its feature exist
In the solvent is deionized water.
7. a kind of cupromanganese plating solution for being used to prepare copper galaxite coating according to claim 1 or 2, its feature exist
In the pH value of the cupromanganese plating solution is 3~7.
8. a kind of method for preparing copper galaxite coating using cupromanganese plating solution as claimed in claim 1 or 2, its feature exist
In this method comprises the following steps：
Step 1: treatment before plating, including oil removal treatment and activation process, detailed process are：
Step 101, oil removal treatment：Alkaline degreaser is heated to 80 DEG C, the alkalescence that then plating metal part is placed in after heating
30min is soaked in degreaser, cleans up and dries after taking-up；The alkaline degreaser includes each component of following concentration：Phosphorus
Sour trisodium 30g/L~40g/L, sodium carbonate 40g/L~50g/L, sodium hydroxide 50g/L~60g/L, sodium metasilicate 5g/L~6g/L,
Surplus is deionized water；
Step 102, activation process：Plating metal part after oil removal treatment in step 101 is placed in the compound acid solution of hydrochloric acid-nitric acid
60s is soaked, is subsequently placed in the dilute sulfuric acid that mass percent concentration is 10%~20% and soaks 60s, cleaned up after taking-up；Institute
The mass percent concentration for stating HCl in the compound acid solution of hydrochloric acid-nitric acid is 20%~30%, HNO3Mass percent concentration be
5%~10%；
Step 2: electroplating processes：Plating metal part after activation process in step 102 is placed in and is loaded with cupromanganese plating solution
In coating bath, using the plating metal part after activation process as negative electrode, using graphite cake as anode, in 20 DEG C~25 DEG C of bath temperature, electricity
Current density is 200mAcm-2~700mAcm-2Under conditions of electroplate 10min~30min, afterwards by the metalwork after plating
Take out, dried up after being cleaned up with deionized water, cupromanganese coating is obtained on metalwork surface；
Step 3: post processing：The plating of cupromanganese described in step 2 is placed in tube furnace, first protected in argon gas atmosphere, temperature
Spend for dehydrogenation 2h under conditions of 800 DEG C, be then in air atmosphere, temperature by the cupromanganese coating after dehydrogenation
Oxidation processes 2h under conditions of 800 DEG C, copper galaxite coating is finally obtained on metalwork surface.
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