CN102912384B - Method for preparing porous copper powder by electrodepositing Cu-Al-Mg-Li alloy - Google Patents
Method for preparing porous copper powder by electrodepositing Cu-Al-Mg-Li alloy Download PDFInfo
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Abstract
The invention discloses a method for preparing porous copper powder by electrodepositing Cu-Al-Mg-Li alloy. The method comprises the steps of preparing a Cu-Al-Mg-Li alloy crude product through electrochemical deposition by taking non-aqueous solution containing lithium salt as an electrolyte, connecting metal copper, metal aluminum and metal magnesium in parallel to be used as an anode and taking a titanium metal sheet as a cathode; carrying out high-energy ball milling on the Cu-Al-Mg-Li alloy crude product, discharging, washing, filtering and drying to obtain Cu-Al-Mg-Li alloy powder; and carrying out acid treatment on the Cu-Al-Mg-Li alloy powder, washing, drying and grinding to obtain porous copper powder. The method has the characteristics of simple process, low energy consumption, no pollution, small equipment investment, low production cost, high production efficiency and the like, can effectively improve production benefits and economic benefits, and is favorable for popularization and application.
Description
Technical field
The present invention relates to a kind of method by galvanic deposit Cu-Al-Mg-Li reasonable offer porous copper powder, belong to metal material field.
Background technology
Copper powder is a kind of important metal powder material, is widely used in the industry such as electrical alloy, electrically conductive ink, electro-conductive adhesive, catalyzer and powder metallurgy.When copper powder is used for catalyst field, the specific surface area of copper powder is one of important indicator evaluating its catalytic performance, and therefore, improving copper powder specific surface area is one of the important research direction in copper powder material preparation science field.
Preparation has the traditional method of the raney copper catalyst of porous matrix structure, it is the hot environment more than 1000 DEG C, after copper, aluminium melting, be processed into copper-aluminium alloy powder, then copper-aluminium alloy powder is used strong caustic process, make aluminium and sodium hydroxide react and dissolve, copper powder then leaves a lot of micropore, each molecule in copper powder is a three-dimensional porous structure, and this vesicular structure makes its specific surface area greatly increase, and drastically increases the catalytic activity of copper powder.What this traditional method prepared X alloy employing is high-temperature melting method, has the shortcomings such as energy consumption is high, facility investment large, pollute greatly, product is oxidizable.Therefore, explore the novel processing step of porous copper powder, to reducing energy consumption, energy-saving and emission-reduction, minimizing facility investment, raising rate of return on investment and enhancing productivity, there is important practical significance.
Summary of the invention
A kind of method by galvanic deposit Cu-Al-Mg-Li reasonable offer porous copper powder of the present invention, object is at normal temperatures and pressures, with the non-aqueous solution containing lithium salts for ionogen, metal copper sheet, metal aluminium flake and metal magnesium sheet are connected in parallel as anode, metal titanium sheet is negative electrode, carries out electrochemical deposition prepare Cu-Al-Mg-Li alloy with power supply; By high-energy ball milling, Cu-Al-Mg-Li alloy is processed into Cu-Al-Mg-Li powdered alloy; Under anaerobic, react remove Al, Mg, Li with Cu-Al-Mg-Li powdered alloy and diluted acid, namely remaining insolubles obtains porous copper powder through washing, vacuum-drying and grinding.The method is carried out at normal temperatures and pressures, therefore have that energy consumption is low, facility investment is little, the advantage such as pollution-free, product non-oxidation, preparation for porous copper powder opens the environmental protection new way of energy-saving and emission-reduction, explores a kind of novel method, has important practical significance.
A kind of method by galvanic deposit Cu-Al-Mg-Li reasonable offer porous copper powder of the present invention, obtained porous copper powder, can be used for the fields such as catalyzer, electrical alloy, electrically conductive ink, electro-conductive adhesive, conductive filler material and powder metallurgy.
A kind of method by galvanic deposit Cu-Al-Mg-Li reasonable offer porous copper powder of the present invention, adopts following technical scheme:
1, containing the preparation of the non-aqueous electrolyte of lithium salts: be (0.1% ~ 95%) according to the mass percent of ionic liquid, high boiling point polar organic solvent, lithium salts, water-resisting agent and fire retardant: (0.1% ~ 95%): (0.001% ~ 50%): (0.001% ~ 10%): the ratio of (0.001% ~ 10%), ionic liquid, high boiling point polar organic solvent, lithium salts, water-resisting agent and fire retardant are mixed, stir the non-aqueous electrolyte obtained containing lithium salts;
2, the galvanic deposit of Cu-Al-Mg-Li alloy: at normal temperatures and pressures, with the non-aqueous solution containing lithium salts for ionogen, metallic copper, metallic aluminium and MAGNESIUM METAL are anode, and copper, aluminium and magnesium three kinds of anodes are connected in parallel, metal titanium sheet is negative electrode, the surface area ratio of copper, aluminium and magnesium three kinds of anodes is (4 ~ 8): (2 ~ 4): (1), and copper, aluminium and magnesium three kinds of anode aerea total are 1: 1 with the ratio of cathode area, and the spacing of negative electrode and positive electrode is 10mm-50mm; Switch on power and carry out electrochemical deposition and prepare Cu-Al-Mg-Li alloy, cathode current density controls at 1 ~ 50A/dm
2, voltage control, at 1 ~ 5V, obtains Cu-Al-Mg-Li alloy by electrodeposit reaction on negative electrode, and interval 5-100min wire brush is by under galvanic deposit product brush, and the galvanic deposit product under brush obtains the thick product of Cu-Al-Mg-Li alloy through washing, filtration and drying;
3, the preparation of Cu-Al-Mg-Li powdered alloy: under argon shield, take dehydrated alcohol as ball-milling medium, in ball mill, the mass ratio (i.e. ratio of grinding media to material) of ball and the thick product of Cu-Al-Mg-Li alloy is (1 ~ 50): 1, the mass ratio (1 ~ 5) of the thick product of Cu-Al-Mg-Li alloy and dehydrated alcohol: 1, be 0.5 ~ 500kW by thick for Cu-Al-Mg-Li alloy product power, ball loadings be 1 ~ 40T, high energy ball mill ball milling 1 ~ 100h that rotating speed is 20 ~ 500r/min, through discharging, washing, filter and be drying to obtain Cu-Al-Mg-Li powdered alloy;
4, the preparation of porous copper powder: the acid of selecting difficult corrosion copper under anaerobic, being mixed with mass percent concentration is 1 ~ 30% aqueous solution, and the equivalent making acid is 1 with the ratio of Al, Mg, Li three total yield in Cu-Al-Mg-Li powdered alloy: (1 ~ 5), pass in dilute acid solution with argon gas, after oxygen in dilute acid solution is got rid of, the dilute acid solution of Cu-Al-Mg-Li powdered alloy and anaerobic is reacted, Al, Mg, Li enter the aqueous solution after being dissolved in acid, after reacting completely, namely remaining insolubles obtains porous copper powder through washing, drying and grinding.
A kind of method by galvanic deposit Cu-Al-Mg-Li reasonable offer porous copper powder of the present invention, has following features:
1, when the aqueous solution of employing salt compounds is ionogen Electrodeposition of metals and alloys, generally all there is liberation of hydrogen problem, the present invention is to contain the non-aqueous solution of lithium salts for ionogen, when preparing Cu-Al-Mg-Li alloy with electrodip process, owing to not containing water in system, therefore there is not the liberation of hydrogen problem of Aquo System, effectively improve current efficiency, reduce energy consumption, improve production efficiency and economic benefit;
2, the active metal such as basic metal, alkaline-earth metal, rare earth metal and aluminium, because it is easy and water reacts, react with water after galvanic deposit out at once, therefore in aqueous electrolyte, galvanic deposit can not prepare the alloy containing active metal, therefore, containing the alloy of active metal, one of its production method adopts the preparation of high-temperature molten salt (generally more than 500 DEG C) electrolytic process, and high temperature fused salt electrolysis method energy consumption is high, equipment corrosion is serious, facility investment is large, environmental pollution is serious; Other conventional production methods of alloy is as vacuum melting method, rapid solidification method, mechanical alloying method and powder metallurgic method etc., generally all there is the technological processs such as high temperature (1000 DEG C-1500 DEG C), vacuum, protection of inert gas in technological process, so, there is the shortcomings such as complex process, energy consumption is high, pollution is large, equipment requirements is high, facility investment is large, production cost is high, production efficiency is low; The present invention is to contain the non-aqueous solution of lithium salts for ionogen, at normal temperatures and pressures, Cu-Al-Mg-Li alloy can be prepared with electrodip process, have that technique is simple, energy consumption is low, pollution-free, facility investment is little, production cost is low, production efficiency high, can effectively improve productivity effect and economic benefit;
3, after introducing metallic lithium in the alloy, due to metallic lithium than MAGNESIUM METAL and metallic aluminium much active, be very easy to be dissolved in acid, even also easily dissolved in weak acid, therefore, Cu-Al-Mg-Li powdered alloy containing metallic lithium, because lithium wherein is very easily dissolved, so, during with acid treatment Cu-Al-Mg-Li powdered alloy, first lithium is discharged the space occupied by it by acid dissolve, add the contact area of Al and Mg and acid solution, be conducive to acid solution to infiltrate fast Al and Mg is dissolved, greatly enhance productivity;
4, ionic liquid has that chemical stability is high, thermostability is high, steam forces down, difficulty is fired, good conductivity, electrochemical window are wide, asepsis environment-protecting, the advantage such as can be recycled, be well suited for being applied to electrochemical deposition of metal or alloy as ionogen, but it is little to the solubleness of lithium salts, therefore the present invention uses high boiling point polar organic solvent in containing the non-aqueous electrolyte of lithium salts, effectively can improve the solubleness of lithium salts, make the concentration of lithium salts reach requirement;
5, in containing the non-aqueous electrolyte of lithium salts, use water-resisting agent, the non-aqueous electrolyte containing lithium salts effectively can be stoped to absorb water from air, improve electrolytical work-ing life;
6, in containing the non-aqueous electrolyte of lithium salts, use fire retardant, can effectively improve electrolytical thermotolerance, improve production security.
7, when with Al, Mg and Li in acid dissolve Cu-Al-Mg-Li powdered alloy, when there being oxygen in acid solution, acid can react with copper and copper corrosion be fallen, and productive rate is declined, and the present invention adopts argon gas by the oxygen expeling in acid solution, can prevent the sour corrosion to copper.
A kind of method by galvanic deposit Cu-Al-Mg-Li reasonable offer porous copper powder of the present invention, ionic liquid used is 1-methyl-3-ethyl imidazol(e) hexafluorophosphate, 1-methyl-3-butyl imidazole hexafluorophosphate, 1-methyl-3-hexyl imidazolium hexafluorophosphate, 1,2-dimethyl-3-ethyl imidazol(e) hexafluorophosphate, 1,2-dimethyl-3-butyl imidazole hexafluorophosphate, 1,2-dimethyl-3-hexyl imidazolium hexafluorophosphate, N-ethylpyridine hexafluorophosphate, N-butyl-pyridinium hexafluorophosphate, 1-methyl-3-ethyl imidazol(e) a tetrafluoro borate, 1-methyl-3-butyl imidazole a tetrafluoro borate, 1-methyl-3-hexyl imidazolium a tetrafluoro borate, 1,2-dimethyl-3-ethyl imidazol(e) a tetrafluoro borate, 1,2-dimethyl-3-butyl imidazole a tetrafluoro borate, 1,2-dimethyl-3-hexyl imidazolium a tetrafluoro borate, N-ethylpyridine a tetrafluoro borate, N-butyl-pyridinium a tetrafluoro borate, any one or more in N-hexyl pyridine hexafluorophosphate and N-hexyl pyridinium tetrafluoroborate salt.
A kind of method by galvanic deposit Cu-Al-Mg-Li reasonable offer porous copper powder of the present invention, high boiling point polar organic solvent used is any one or more in DMF, propylene carbonate, dimethyl sulfoxide (DMSO).
A kind of method by galvanic deposit Cu-Al-Mg-Li reasonable offer porous copper powder of the present invention, lithium salts used is any one or more in LiBF4, lithium hexafluoro phosphate, lithium chloride, Lithium Acetate, lithium formate.
A kind of method by galvanic deposit Cu-Al-Mg-Li reasonable offer porous copper powder of the present invention, water-resisting agent used is any one or more in whiteruss, dimethyl silicone oil, diethyl silicone oil.
A kind of method by galvanic deposit Cu-Al-Mg-Li reasonable offer porous copper powder of the present invention, fire retardant used is any one or more in triethyl phosphate, trimethyl phosphite 99, tributyl phosphate, triphenylphosphate, Tritolyl Phosphate.
A kind of method by galvanic deposit Cu-Al-Mg-Li reasonable offer porous copper powder of the present invention, dissolving Al, Mg and Li in Cu-Al-Mg-Li alloy acid used is any one or more in hydrochloric acid, sulfuric acid, acetic acid, formic acid, propionic acid.
A kind of method by galvanic deposit Cu-Al-Mg-Li reasonable offer porous copper powder of the present invention, power supply used is voltage is 1 ~ 30V, and electric current is any one in the direct supply of 1 ~ 5000A, monopulse direct supply and two pulse direct supply.
A kind of method by galvanic deposit Cu-Al-Mg-Li reasonable offer porous copper powder of the present invention, ball mill used is power is 0.5 ~ 500kW, ball loadings is 1 ~ 40T, rotating speed is the high energy ball mill of 20 ~ 500r/min.
Embodiment
Here is a kind of non-limiting example by the method for galvanic deposit Cu-Al-Mg-Li reasonable offer porous copper powder of the present invention.The providing of these examples is only used to the object illustrated, can not be interpreted as limitation of the invention.Because without departing from the spirit and scope of the present invention, many conversion can be carried out to the present invention.In these embodiments, unless stated otherwise, all per-cent all refers to mass percent.
Embodiment 1
Containing the preparation of the non-aqueous electrolyte of lithium salts
1-methyl-3-ethyl imidazol(e) hexafluorophosphate: 35%
1-methyl-3-butyl imidazole a tetrafluoro borate: 30%
N-butyl-pyridinium hexafluorophosphate: 10%
DMF: 12%
Propylene carbonate: 2%
LiBF4: 7%
Lithium Acetate: 1%
Whiteruss 0.5%
Triethyl phosphate 2.5%
According to above-mentioned mass percent, by 1-methyl-3-ethyl imidazol(e) hexafluorophosphate, 1-methyl-3-butyl imidazole a tetrafluoro borate, N-butyl-pyridinium hexafluorophosphate, N, dinethylformamide, propylene carbonate, LiBF4, Lithium Acetate, whiteruss and triethyl phosphate mix, and stir the non-aqueous electrolyte obtained containing lithium salts;
The galvanic deposit of Cu-Al-Mg-Li alloy
At normal temperatures and pressures, with the non-aqueous solution containing lithium salts for ionogen, metallic copper, metallic aluminium and MAGNESIUM METAL are anode, and copper, aluminium and magnesium three kinds of anodes are connected in parallel, metal titanium sheet is negative electrode, the surface area ratio of copper, aluminium and magnesium three kinds of anodes is 4: 3: 1, and copper, aluminium and magnesium three kinds of anode aerea total are 1: 1 with the ratio of cathode area, and the spacing of negative electrode and positive electrode is 20mm; Take voltage as 5V, electric current is the direct supply of 200A is power supply, switches on power to carry out electrochemical deposition and prepare Cu-Al-Mg-Li alloy, and cathode current density controls at 2.5A/dm
2left and right, voltage control is at about 3.2V, on negative electrode, obtain Cu-Al-Mg-Li alloy by electrodeposit reaction, interval 10min wire brush is by under galvanic deposit product brush, and the galvanic deposit product under brush obtains the thick product of Cu-Al-Mg-Li alloy through washing, filtration and drying;
The preparation of Cu-Al-Mg-Li powdered alloy
Ball mill is power is 0.5 ~ 500kW, ball loadings is 1 ~ 40T, rotating speed is that the high energy ball mill of 20 ~ 500r/min is under argon shield, take dehydrated alcohol as ball-milling medium, in ball mill, the mass ratio (i.e. ratio of grinding media to material) of ball and the thick product of Cu-Al-Mg-Li alloy is 25: 1, the mass ratio 2.5: 1 of the thick product of Cu-Al-Mg-Li alloy and dehydrated alcohol, be 11kW by thick for Cu-Al-Mg-Li alloy product power, ball loadings is 0.9T, rotating speed is the high energy ball mill ball milling 50h of 38r/min, through discharging, washing, filter and be drying to obtain Cu-Al-Mg-Li powdered alloy,
The preparation of porous copper powder
Preparation mass percent concentration is 5% aqueous hydrochloric acid, and the equivalent making acid is 1: 1.3 with the ratio of Al, Mg, Li three total yield in Cu-Al-Mg-Li powdered alloy, with argon gas, the oxygen in acid solution is driven away, to prevent the corrosion of acid to copper, Cu-Al-Mg-Li powdered alloy and aqueous acid are reacted, enter the aqueous solution after making Al, Mg, Li be dissolved in acid, after reacting completely, namely remaining insolubles obtains porous copper powder through washing, drying and grinding.
Embodiment 2
Containing the preparation of the non-aqueous electrolyte of lithium salts
N-ethylpyridine a tetrafluoro borate: 20%
1-methyl-3-butyl imidazole hexafluorophosphate: 20%
1-methyl-3-ethyl imidazol(e) a tetrafluoro borate: 20%
1,2-dimethyl-3-ethyl imidazol(e) hexafluorophosphate: 10%
Propylene carbonate: 5%
Dimethyl sulfoxide (DMSO): 15%
Lithium hexafluoro phosphate: 6%
Paraffin: 1%
Dimethyl silicone oil: 0.5%
Trimethyl phosphite 99: 0.5%
Tributyl phosphate: 2%
According to above-mentioned mass percent, by N-ethylpyridine a tetrafluoro borate, 1-methyl-3-butyl imidazole hexafluorophosphate, 1-methyl-3-ethyl imidazol(e) a tetrafluoro borate, 1,2-dimethyl-3-ethyl imidazol(e) hexafluorophosphate, propylene carbonate, dimethyl sulfoxide (DMSO), lithium hexafluoro phosphate, paraffin, dimethyl silicone oil, trimethyl phosphite 99 and tributyl phosphate mix, and stir the non-aqueous electrolyte obtained containing lithium salts;
The galvanic deposit of Cu-Al-Mg-Li alloy
At normal temperatures and pressures, with the non-aqueous solution containing lithium salts for ionogen, metallic copper, metallic aluminium and MAGNESIUM METAL are anode, and copper, aluminium and magnesium three kinds of anodes are connected in parallel, metal titanium sheet is negative electrode, the surface area ratio of copper, aluminium and magnesium three kinds of anodes is 5: 4: 1, and copper, aluminium and magnesium three kinds of anode aerea total are 1: 1 with the ratio of cathode area, and the spacing of negative electrode and positive electrode is 30mm; Take voltage as 10V, electric current is the monopulse direct supply of 300A is power supply, switches on power to carry out electrochemical deposition and prepare Cu-Al-Mg-Li alloy, and cathode current density controls at 2A/dm
2left and right, voltage control is at about 3.3V, on negative electrode, obtain Cu-Al-Mg-Li alloy by electrodeposit reaction, interval 15min wire brush is by under galvanic deposit product brush, and the galvanic deposit product under brush obtains the thick product of Cu-Al-Mg-Li alloy through washing, filtration and drying;
The preparation of Cu-Al-Mg-Li powdered alloy
Under argon shield, take dehydrated alcohol as ball-milling medium, in ball mill, the mass ratio (i.e. ratio of grinding media to material) of ball and the thick product of Cu-Al-Mg-Li alloy is 30: 1, the mass ratio 2: 1 of the thick product of Cu-Al-Mg-Li alloy and dehydrated alcohol, be 15kW by thick for Cu-Al-Mg-Li alloy product power, ball loadings be 1.3T, high energy ball mill ball milling 60h that rotating speed is 35r/min, through discharging, washing, filter and be drying to obtain Cu-Al-Mg-Li powdered alloy;
The preparation of porous copper powder
Preparation mass percent concentration is 15% aqueous sulfuric acid, and the equivalent making acid is 1: 1.2 with the ratio of Al, Mg, Li three total yield in Cu-Al-Mg-Li powdered alloy, with argon gas, the oxygen in acid solution is driven away, to prevent the corrosion of acid to copper, Cu-Al-Mg-Li powdered alloy and aqueous acid are reacted, enter the aqueous solution after making Al, Mg, Li be dissolved in acid, after reacting completely, namely remaining insolubles obtains porous copper powder through washing, drying and grinding.
Embodiment 3
Containing the preparation of the non-aqueous electrolyte of lithium salts
1,2-dimethyl-3-ethyl imidazol(e) a tetrafluoro borate: 30%
1,2-dimethyl-3-butyl imidazole hexafluorophosphate: 30%
N-butyl-pyridinium a tetrafluoro borate: 15%
Dimethyl sulfoxide (DMSO): 8%
Lithium formate: 2%
Lithium hexafluoro phosphate: 12%
Diethyl silicone oil: 0.5%
Triethyl phosphate: 2%
Triphenylphosphate: 0.5%
According to above-mentioned mass percent, by 1,2-dimethyl-3-ethyl imidazol(e) a tetrafluoro borate, 1,2-dimethyl-3-butyl imidazole hexafluorophosphate, N-butyl-pyridinium a tetrafluoro borate, dimethyl sulfoxide (DMSO), lithium formate, lithium hexafluoro phosphate, diethyl silicone oil, triethyl phosphate and triphenylphosphate mix, and stir the non-aqueous electrolyte obtained containing lithium salts;
The galvanic deposit of Cu-Al-Mg-Li alloy
At normal temperatures and pressures, with the non-aqueous solution containing lithium salts for ionogen, metallic copper, metallic aluminium and MAGNESIUM METAL are anode, and copper, aluminium and magnesium three kinds of anodes are connected in parallel, metal titanium sheet is negative electrode, the surface area ratio of copper, aluminium and magnesium three kinds of anodes is 6: 3: 1, and copper, aluminium and magnesium three kinds of anode aerea total are 1: 1 with the ratio of cathode area, and the spacing of negative electrode and positive electrode is 40mm; Take voltage as 15V, electric current is the two pulse direct supply of 500A is power supply, switches on power to carry out electrochemical deposition and prepare Cu-Al-Mg-Li alloy, and cathode current density controls at 1.5A/dm
2left and right, voltage control is at about 3.4V, on negative electrode, obtain Cu-Al-Mg-Li alloy by electrodeposit reaction, interval 20min wire brush is by under galvanic deposit product brush, and the galvanic deposit product under brush obtains the thick product of Cu-Al-Mg-Li alloy through washing, filtration and drying;
The preparation of Cu-Al-Mg-Li powdered alloy
Under argon shield, take dehydrated alcohol as ball-milling medium, in ball mill, the mass ratio (i.e. ratio of grinding media to material) of ball and the thick product of Cu-Al-Mg-Li alloy is 35: 1, the mass ratio 3: 1 of the thick product of Cu-Al-Mg-Li alloy and dehydrated alcohol, be 8kW by thick for Cu-Al-Mg-Li alloy product power, ball loadings be 0.6T, high energy ball mill ball milling 80h that rotating speed is 50r/min, through discharging, washing, filter and be drying to obtain Cu-Al-Mg-Li powdered alloy;
The preparation of porous copper powder
Preparation mass percent concentration is the mixed acid aqueous solution of 5% sulfuric acid and 5% acetic acid, and the equivalent making acid is 1: 1.4 with the ratio of Al, Mg, Li three total yield in Cu-Al-Mg-Li powdered alloy, with argon gas, the oxygen in acid solution is driven away, to prevent the corrosion of acid to copper, Cu-Al-Mg-Li powdered alloy and aqueous acid are reacted, enter the aqueous solution after making Al, Mg, Li be dissolved in acid, after reacting completely, namely remaining insolubles obtains porous copper powder through washing, drying and grinding.
Claims (7)
1., by a method for galvanic deposit Cu-Al-Mg-Li reasonable offer porous copper powder, it is characterized in that adopting following technical scheme and step to be prepared:
1. containing the preparation of non-aqueous electrolyte of lithium salts: be (0.1% ~ 95%) according to the mass percent of ionic liquid, high boiling point polar organic solvent, lithium salts, water-resisting agent and fire retardant: (0.1% ~ 95%): (0.001% ~ 50%): (0.001% ~ 10%): the ratio of (0.001% ~ 10%), ionic liquid, high boiling point polar organic solvent, lithium salts, water-resisting agent and fire retardant are mixed, stir the non-aqueous electrolyte obtained containing lithium salts;
2. the galvanic deposit of Cu-Al-Mg-Li alloy: at normal temperatures and pressures, with the non-aqueous solution containing lithium salts for ionogen, metallic copper, metallic aluminium and MAGNESIUM METAL are anode, and copper, aluminium and magnesium three kinds of anodes are connected in parallel, metal titanium sheet is negative electrode, the surface area ratio of copper, aluminium and magnesium three kinds of anodes is (4 ~ 8): (2 ~ 4): (1), and copper, aluminium and magnesium three kinds of anode aerea total are 1: 1 with the ratio of cathode area, and the spacing of negative electrode and positive electrode is 10mm-50mm; Switch on power and carry out electrochemical deposition and prepare Cu-Al-Mg-Li alloy, cathode current density controls at 1 ~ 50A/dm
2, voltage control, at 1 ~ 5V, obtains Cu-Al-Mg-Li alloy by electrodeposit reaction on negative electrode, and interval 5-100min wire brush is by under galvanic deposit product brush, and the galvanic deposit product under brush obtains the thick product of Cu-Al-Mg-Li alloy through washing, filtration and drying;
3. the preparation of Cu-Al-Mg-Li powdered alloy: under argon shield, take dehydrated alcohol as ball-milling medium, in ball mill, the mass ratio (i.e. ratio of grinding media to material) of ball and the thick product of Cu-Al-Mg-Li alloy is (1 ~ 50): 1, the mass ratio (1 ~ 5) of the thick product of Cu-Al-Mg-Li alloy and dehydrated alcohol: 1, be 0.5 ~ 500kW by thick for Cu-Al-Mg-Li alloy product power, ball loadings be 1 ~ 40T, high energy ball mill ball milling 1 ~ 100h that rotating speed is 20 ~ 500r/min, through discharging, washing, filter and be drying to obtain Cu-Al-Mg-Li powdered alloy;
4. the preparation of porous copper powder: the acid of selecting difficult corrosion copper under anaerobic, being mixed with mass percent concentration is 1 ~ 30% aqueous solution, and the equivalent making acid is 1 with the ratio of Al, Mg, Li three total yield in Cu-Al-Mg-Li powdered alloy: (1 ~ 5), pass in dilute acid solution with argon gas, after oxygen in dilute acid solution is got rid of, the dilute acid solution of Cu-Al-Mg-Li powdered alloy and anaerobic is reacted, Al, Mg, Li enter the aqueous solution after being dissolved in acid, after reacting completely, namely remaining insolubles obtains porous copper powder through washing, drying and grinding.
2. preparation method as claimed in claim 1, it is characterized in that ionic liquid used is 1-methyl-3-ethyl imidazol(e) hexafluorophosphate, 1-methyl-3-butyl imidazole hexafluorophosphate, 1-methyl-3-hexyl imidazolium hexafluorophosphate, 1, 2-dimethyl-3-ethyl imidazol(e) hexafluorophosphate, 1, 2-dimethyl-3-butyl imidazole hexafluorophosphate, 1, 2-dimethyl-3-hexyl imidazolium hexafluorophosphate, N-ethylpyridine hexafluorophosphate, N-butyl-pyridinium hexafluorophosphate, 1-methyl-3-ethyl imidazol(e) a tetrafluoro borate, 1-methyl-3-butyl imidazole a tetrafluoro borate, 1-methyl-3-hexyl imidazolium a tetrafluoro borate, 1, 2-dimethyl-3-ethyl imidazol(e) a tetrafluoro borate, 1, 2-dimethyl-3-butyl imidazole a tetrafluoro borate, 1, 2-dimethyl-3-hexyl imidazolium a tetrafluoro borate, N-ethylpyridine a tetrafluoro borate, N-butyl-pyridinium a tetrafluoro borate, any one or more in N-hexyl pyridine hexafluorophosphate and N-hexyl pyridinium tetrafluoroborate salt.
3. preparation method as claimed in claim 1, is characterized in that high boiling point polar organic solvent used is any one or more in DMF, propylene carbonate, dimethyl sulfoxide (DMSO).
4. preparation method as claimed in claim 1, is characterized in that lithium salts used is any one or more in LiBF4, lithium hexafluoro phosphate, lithium chloride, Lithium Acetate, lithium formate.
5. preparation method as claimed in claim 1, is characterized in that water-resisting agent used is any one or more in whiteruss, dimethyl silicone oil, diethyl silicone oil.
6. preparation method as claimed in claim 1, is characterized in that fire retardant used is any one or more in triethyl phosphate, trimethyl phosphite 99, tributyl phosphate, triphenylphosphate, Tritolyl Phosphate.
7. preparation method as claimed in claim 1, it is characterized in that dissolving Al, Mg and Li in Cu-Al-Mg-Li alloy acid used is any one or more in hydrochloric acid, sulfuric acid, acetic acid, formic acid, propionic acid.
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