CN104928724B - A kind of method of the electrolytic preparation dendroid fine copper powder in ethanedioic acid - Google Patents
A kind of method of the electrolytic preparation dendroid fine copper powder in ethanedioic acid Download PDFInfo
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- CN104928724B CN104928724B CN201510391482.2A CN201510391482A CN104928724B CN 104928724 B CN104928724 B CN 104928724B CN 201510391482 A CN201510391482 A CN 201510391482A CN 104928724 B CN104928724 B CN 104928724B
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- copper powder
- fine copper
- ethanedioic acid
- negative electrode
- dendroid
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 241000555268 Dendroides Species 0.000 title claims abstract description 65
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 title claims abstract description 55
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 35
- 239000003792 electrolyte Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 239000010936 titanium Substances 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims description 30
- 238000005868 electrolysis reaction Methods 0.000 claims description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 238000003795 desorption Methods 0.000 claims description 9
- 238000007670 refining Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 27
- 238000009826 distribution Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000009856 non-ferrous metallurgy Methods 0.000 abstract description 2
- 238000001291 vacuum drying Methods 0.000 abstract 1
- 230000005611 electricity Effects 0.000 description 8
- NIFHFRBCEUSGEE-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O.OC(=O)C(O)=O NIFHFRBCEUSGEE-UHFFFAOYSA-N 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000009790 rate-determining step (RDS) Methods 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Electrolytic Production Of Metals (AREA)
Abstract
The present invention relates to a kind of method of the electrolytic preparation dendroid fine copper powder in ethanedioic acid, belong to non-ferrous metallurgy technology field.To adding ethanedioic acid to form the ethanedioic acid solution that concentration is 0.1~0.5mol/L in pure water, then the mol ratio according to ethanedioic acid in ethanedioic acid solution and auxiliary reagent is 1:1 adds auxiliary reagent, and electrolyte is obtained after being well mixed；Electrolyte is heated to 20~50 DEG C, then pure copper anode and titanium sheet negative electrode is placed in electrolyte and is electrolysed, fine copper powder can be deposited on negative electrode；Removed fine copper powder is deposited on negative electrode, cleaned with pure water 3 times, through 60~80 DEG C of vacuum drying, obtain the dendroid fine copper powder that granularity is 10~20 μm.The method can obtain the narrow fine copper powder of particle size distribution by simple method, and electrolyte system is environment-friendly, cheap and easy to get.
Description
Technical field
The present invention relates to a kind of method of the electrolytic preparation dendroid fine copper powder in ethanedioic acid, belong to Non-ferrous Metallurgy
Technical field.
Background technology
Copper powder has good conduction, thermal conductance and briquettability, plasticity and sintering character, be automobile, space flight and aviation,
The indispensable and irreplaceable metal powder material in the field such as machinery, chemical industry, the energy and 3C industries.With the hair of science and technology
Exhibition, copper powder changes via metal powder material to functional material, particularly in recent years, with the development of 3D printing technique,
Copper powder turns into a kind of important printing raw material, with the irreplaceable effect of other powder.
Copper powder preparation method is roughly divided into Physical, solution phase chemical reduction and electrolysis three major types, and Physical is divided into again
Physical evaporation-condensation method, mechanical disruption method and atomization etc..Physical evaporation-condensation method can prepare that sphericity is high, inoxidizability
Can preferably and the tiny copper powder of particle diameter, but the particle size distribution of copper powder is larger, and equipment used is sufficiently expensive, is produced into
This height.Copper powder particle size skewness prepared by mechanical disruption method, reunites more serious, and pattern is difficult to control to, easily oxidation, and
And the production cycle is long, energy consumption is big, is restricted in terms of high-end copper powder is produced.Copper powder prepared by atomization is spherical in shape, and particle diameter leads to
Often in micron order.Solution phase chemical reduction can prepare the relatively fine copper powder of particle diameter, and can control the size distribution of copper powder, but need choosing
Suitable reducing agent is selected, the compound of copper, copper ion or cuprous ion etc. copper powder is reduced in aqueous, in preparation process
Required reagent type is more, it is complex to operate, and is limited by reducing agent species and cost, and the reducing agent commonly used is such as
NaBH4, ascorbic acid, glucose, hypophosphorous acid, quinhydrones, formaldehyde, in hydrazine hydrate etc. some there is toxicity, some are expensive, therefore
And a small amount of copper powder can only be on a small scale prepared, fairly large industrial production should not be carried out.Because the copper powder of electrolysis production has
Purity is high, specific surface area is big, compressibility and the advantages of good moldability, is currently the main stream approach for producing copper powder.Electricity in the aqueous solution
Solution production copper powder is needed in low copper ion concentration and the electricity of high acid concentration generally using copper sulphate+sulfuric acid as electrolyte during electrolysis
In solution liquid, control cathode-current density is in 1200~2000A/m2Under conditions of carry out so that the concentration difference of cathode surface copper ion
Polarization, promotes the generation of copper powder.The concentration polarization of copper ion necessarily causes cathodic polarization and cathode surface that violent liberation of hydrogen occurs
Side reaction, so when electrolytic copper powder is carried out, current efficiency only about 30% is, it is necessary to consume substantial amounts of electric energy, low current efficiency is not
The yield of unit interval copper powder is reduced by only, while also substantially increasing the preparation cost of copper powder.
Patent CN101560674A carries out electrolytic preparation in super gravity field and goes out average grain diameter in 20 μm or so of copper powder, borrows
Hypergravity is helped to increase Cu2+To the diffusion rate of electrode surface, reduce electrode surface Cu2+Concentration polarization, improve electrolytic copper powder
Current efficiency is to 55%~74%.Patent CN101007354A directly carries out ore pulp electricity using ultrasonic membrane electrolysis with copper concentrate
Solution, prepares granularity less than 4 μm of superfine cupper powders, can shorten metallurgical and material work flow, the copper powder that the method is obtained mostly ball
Shape, but because raw material is copper concentrate, complicated component, gained copper powder is 98.8% containing Cu.Patent CN 101717971B utilize sulfuric acid
The mixed solution of copper, phosphoric acid, gelatin and benzotriazole as electrolyte, in 300~800A/m2Current density under, electrolysis
Fine copper powder of the particle diameter at 2.5~7.5 μm is prepared, 17%~45%, power consumption is generally higher than 15000 (kWh) to current efficiency
Copper powder per ton.The ChCl-Urea eutectic solvent type ionic liquids that inventor was once formed using Choline Chloride with urea mixing congruent melting
Body as electrolyte, with fine copper as anode, titanium sheet or stainless steel plate as negative electrode, dendroid fine copper powder has been electrolysed out, during electrolysis
The current density of control is only 50A/m2, and current efficiency is up to 95%.ChCl-Urea eutectic solvent type ionic liquids have
Electrochemical window is wide, and the characteristics of stable system, but the price of preparing raw material is higher than ethanedioic acid.
The content of the invention
For problem and deficiency that above-mentioned prior art is present, the present invention provides one kind electrolytic preparation branch in ethanedioic acid
The method of shape fine copper powder.The method can obtain the narrow fine copper powder of particle size distribution, and electrolysis by simple method
Plastidome is environment-friendly, cheap and easy to get, significantly reduces the power consumption and production cost of electrolysis production copper powder, the present invention by with
Lower technical scheme is realized.
A kind of method of the electrolytic preparation dendroid fine copper powder in ethanedioic acid, it is comprised the following steps that：
Step 1, to adding ethanedioic acid to form the ethanedioic acid solution that concentration is 0.1~0.5mol/L, then basis in pure water
Ethanedioic acid and the mol ratio of auxiliary reagent are 1 in ethanedioic acid solution:1 adds auxiliary reagent, and electrolyte is obtained after being well mixed；
Step 2, the electrolyte that step 1 is obtained is heated to 20~50 DEG C, is then placed in pure copper anode and titanium sheet negative electrode
It is (1~2) in the area ratio for stirring, controlling anode and negative electrode in electrolyte:1st, negative and positive die opening is 20~50mm, direct current
Current density is 50~300A/m2Under the conditions of be electrolysed 30~120min, fine copper powder can be deposited on negative electrode；
Step 3, will on step 2 negative electrode deposit fine copper powder remove, clean with pure water 3 times, through 60~80 DEG C be vacuum dried,
Obtain the dendroid fine copper powder that granularity is 10~20 μm.
Auxiliary reagent in the step 1 is one or several in ammoniacal liquor, ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate
Meaning scalemic thereof.
Pure copper anode is the standard cathode copper or Cu-CATH-1 of aqueous solution electrolysis refining institute output in the step 2.
Titanium sheet negative electrode is TA1 or TA2 in the step 2.
Depositing the process removed of fine copper powder in the step 3 on negative electrode is：The negative electrode of fine copper powder will be deposited from electrolysis
After being taken out in groove, it is put into pure water quickly, ultrasonic desorption, dispersion, cleaning is carried out by ultrasonic cleaner, ultrasonic time is
10~60min.
The beneficial effects of the invention are as follows：
（1）Compared with traditional aqueous system electrolytic copper powder, current efficiency is greatly improved the present invention, and up to 90.5%,
Power consumption is significantly reduced, and lowest energy consumption is 2994 (kWh) t-1, this technology can using lower current density 50~
300A/m2, and traditional aqueous electrolytic copper powder is then 1200~2000A/m2。
（2）Electrolyte ethanedioic acid of the invention has reproducibility so that the copper powder produced in electrolytic process is difficult to be oxidized,
Serve obvious antioxidation.
（3）Copper powder size prepared by the present invention is 10~20 μm, and epigranular, pattern is dendroid, with wider
Applicability.
（4）Raw material ethanedioic acid of the present invention is general chemical product and raw material, is usually used in detergent, bleaching agent day
Deng inexpensive, nontoxic pollution-free also can be recycled, and auxiliary reagent is common chemical reagent.
Brief description of the drawings
Fig. 1 is process chart of the invention；
Fig. 2 is the dendroid fine copper powder SEM photograph figure A that the embodiment of the present invention 4 is prepared；
Fig. 3 is the dendroid fine copper powder SEM photograph figure B that the embodiment of the present invention 4 is prepared；
Fig. 4 is the particle size distribution figure of the dendroid fine copper powder that the embodiment of the present invention 4 is prepared.
Specific embodiment
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
As shown in figure 1, the method for being somebody's turn to do the electrolytic preparation dendroid fine copper powder in ethanedioic acid, it is comprised the following steps that：
Step 1, in pure water add ethanedioic acid formed concentration for 0.1mol/L ethanedioic acid solution, then according to ethanedioic acid
Ethanedioic acid and the mol ratio of auxiliary reagent are 1 in solution:1 adds auxiliary reagent, and electrolyte is obtained after being well mixed；Wherein aid in
Reagent is 1.2g ammonium chlorides；
Step 2, the 220mL electrolyte for obtaining step 1 are heated to 40 DEG C, are then placed in pure copper anode and titanium sheet negative electrode
In electrolyte, stir speed (S.S.) be 500r/min, control anode and negative electrode area ratio be 1:1st, negative and positive die opening is 50mm, straight
Galvanic current density is 75A/m2Under the conditions of be electrolysed 120min, fine copper powder can be deposited on negative electrode；Wherein pure copper anode is
The standard cathode copper of aqueous solution electrolysis refining institute output, titanium sheet negative electrode is TA1；
Step 3, will on step 2 negative electrode deposit fine copper powder remove, clean with pure water 3 times, through 80 DEG C be vacuum dried 2h, obtain
The process that fine copper powder removes is deposited to the dendroid fine copper powder that granularity is 11~18 μm, wherein on negative electrode is：To deposit micro-
After the negative electrode of thin copper powder takes out from electrolytic cell, it is put into pure water quickly, carries out ultrasonic desorption by ultrasonic cleaner, divides
Dissipate, clean, ultrasonic time is 10min.
The dendroid fine copper powder pattern for preparing is dendroid, and copper powder particle size is uniform.Direct current consumption is 3059 (kW
h)·t-1, current efficiency is 83.5%.
Embodiment 2
As shown in figure 1, the method for being somebody's turn to do the electrolytic preparation dendroid fine copper powder in ethanedioic acid, it is comprised the following steps that：
Step 1, in pure water add ethanedioic acid formed concentration for 0.2mol/L ethanedioic acid solution, then according to ethanedioic acid
Ethanedioic acid and the mol ratio of auxiliary reagent are 1 in solution:1 adds auxiliary reagent, and electrolyte is obtained after being well mixed；Wherein aid in
Reagent is 2.4g ammonium chlorides；
Step 2, the 220mL electrolyte for obtaining step 1 are heated to 40 DEG C, are then placed in pure copper anode and titanium sheet negative electrode
In electrolyte, stir speed (S.S.) be 500r/min, control anode and negative electrode area ratio be 1:1st, negative and positive die opening is 50mm, straight
Galvanic current density is 75A/m2Under the conditions of be electrolysed 120min, fine copper powder can be deposited on negative electrode；Wherein pure copper anode is
The standard cathode copper of aqueous solution electrolysis refining institute output, titanium sheet negative electrode is TA1；
Step 3, will on step 2 negative electrode deposit fine copper powder remove, clean with pure water 3 times, through 80 DEG C be vacuum dried 2h, obtain
The process that fine copper powder removes is deposited to the dendroid fine copper powder that granularity is 12~16 μm, wherein on negative electrode is：To deposit micro-
After the negative electrode of thin copper powder takes out from electrolytic cell, it is put into pure water quickly, carries out ultrasonic desorption by ultrasonic cleaner, divides
Dissipate, clean, ultrasonic time is 10min.
The dendroid fine copper powder pattern for preparing is dendroid, and copper powder particle size is uniform.Direct current consumption is 3039 (kW
h)·t-1, current efficiency is 86.0%.
Embodiment 3
As shown in figure 1, the method for being somebody's turn to do the electrolytic preparation dendroid fine copper powder in ethanedioic acid, it is comprised the following steps that：
Step 1, in pure water add ethanedioic acid formed concentration for 0.3mol/L ethanedioic acid solution, then according to ethanedioic acid
Ethanedioic acid and the mol ratio of auxiliary reagent are 1 in solution:1 adds auxiliary reagent, and electrolyte is obtained after being well mixed；Wherein aid in
Reagent is 3.5g ammonium chlorides；
Step 2, the 220mL electrolyte for obtaining step 1 are heated to 40 DEG C, are then placed in pure copper anode and titanium sheet negative electrode
In electrolyte, stir speed (S.S.) be 500r/min, control anode and negative electrode area ratio be 1:1st, negative and positive die opening is 50mm, straight
Galvanic current density is 75A/m2Under the conditions of be electrolysed 120min, fine copper powder can be deposited on negative electrode；Wherein pure copper anode is
The standard cathode copper of aqueous solution electrolysis refining institute output, titanium sheet negative electrode is TA1；
Step 3, will on step 2 negative electrode deposit fine copper powder remove, clean with pure water 3 times, through 80 DEG C be vacuum dried 2h, obtain
The process that fine copper powder removes is deposited to the dendroid fine copper powder that granularity is 12~18 μm, wherein on negative electrode is：To deposit micro-
After the negative electrode of thin copper powder takes out from electrolytic cell, it is put into pure water quickly, carries out ultrasonic desorption by ultrasonic cleaner, divides
Dissipate, clean, ultrasonic time is 10min.
The dendroid fine copper powder pattern for preparing is dendroid, and copper powder particle size is uniform.Direct current consumption is 3011 (kW
h)·t-1, current efficiency is 87.1%.
Embodiment 4
As shown in figure 1, the method for being somebody's turn to do the electrolytic preparation dendroid fine copper powder in ethanedioic acid, it is comprised the following steps that：
Step 1, in pure water add ethanedioic acid formed concentration for 0.4mol/L ethanedioic acid solution, then according to ethanedioic acid
Ethanedioic acid and the mol ratio of auxiliary reagent are 1 in solution:1 adds auxiliary reagent, and electrolyte is obtained after being well mixed；Wherein aid in
Reagent is 4.7g ammonium chlorides；
Step 2, the 220mL electrolyte for obtaining step 1 are heated to 40 DEG C, are then placed in pure copper anode and titanium sheet negative electrode
In electrolyte, stir speed (S.S.) be 500r/min, control anode and negative electrode area ratio be 1:1st, negative and positive die opening is 50mm, straight
Galvanic current density is 75A/m2Under the conditions of be electrolysed 120min, fine copper powder can be deposited on negative electrode；Wherein pure copper anode is
The standard cathode copper of aqueous solution electrolysis refining institute output, titanium sheet negative electrode is TA1；
Step 3, will on step 2 negative electrode deposit fine copper powder remove, clean with pure water 3 times, through 80 DEG C be vacuum dried 2h, obtain
The process that fine copper powder removes is deposited to the dendroid fine copper powder that granularity is 12~19 μm, wherein on negative electrode is：To deposit micro-
After the negative electrode of thin copper powder takes out from electrolytic cell, it is put into pure water quickly, carries out ultrasonic desorption by ultrasonic cleaner, divides
Dissipate, clean, ultrasonic time is 10min.
The dendroid fine copper powder SEM photograph figure that the present embodiment is prepared as shown in Figures 2 and 3, dendroid fine copper powder
Particle size distribution figure it is as shown in Figure 4.
The dendroid fine copper powder pattern for preparing is dendroid, and copper powder particle size is uniform.Direct current consumption is 3004
(kW·h)·t-1, current efficiency is 89.2%.
Embodiment 5
As shown in figure 1, the method for being somebody's turn to do the electrolytic preparation dendroid fine copper powder in ethanedioic acid, it is comprised the following steps that：
Step 1, in pure water add ethanedioic acid formed concentration for 0.5mol/L ethanedioic acid solution, then according to ethanedioic acid
Ethanedioic acid and the mol ratio of auxiliary reagent are 1 in solution:1 adds auxiliary reagent, and electrolyte is obtained after being well mixed；Wherein aid in
Reagent is 5.9g ammonium chlorides；
Step 2, the 220mL electrolyte for obtaining step 1 are heated to 40 DEG C, are then placed in pure copper anode and titanium sheet negative electrode
In electrolyte, stir speed (S.S.) be 500r/min, control anode and negative electrode area ratio be 1:1st, negative and positive die opening is 50mm, straight
Galvanic current density is 75A/m2Under the conditions of be electrolysed 120min, fine copper powder can be deposited on negative electrode；Wherein pure copper anode is
The standard cathode copper of aqueous solution electrolysis refining institute output, titanium sheet negative electrode is TA1；
Step 3, will on step 2 negative electrode deposit fine copper powder remove, clean with pure water 3 times, through 80 DEG C be vacuum dried 2h, obtain
The process that fine copper powder removes is deposited to the dendroid fine copper powder that granularity is 15~20 μm, wherein on negative electrode is：To deposit micro-
After the negative electrode of thin copper powder takes out from electrolytic cell, it is put into pure water quickly, carries out ultrasonic desorption by ultrasonic cleaner, divides
Dissipate, clean, ultrasonic time is 10min.
The dendroid fine copper powder pattern for preparing is dendroid, and copper powder particle size is uniform.Direct current consumption is 2994 (kW
h)·t-1, current efficiency is 89.7%.
Embodiment 6
As shown in figure 1, the method for being somebody's turn to do the electrolytic preparation dendroid fine copper powder in ethanedioic acid, it is comprised the following steps that：
Step 1, in pure water add ethanedioic acid formed concentration for 0.4mol/L ethanedioic acid solution, then according to ethanedioic acid
Ethanedioic acid and the mol ratio of auxiliary reagent are 1 in solution:1 adds auxiliary reagent, and electrolyte is obtained after being well mixed；Wherein aid in
Reagent is 4.7g ammonium chlorides；
Step 2, the 220mL electrolyte for obtaining step 1 are heated to 20 DEG C, are then placed in pure copper anode and titanium sheet negative electrode
In electrolyte, stir speed (S.S.) be 500r/min, control anode and negative electrode area ratio be 1:1st, negative and positive die opening is 50mm, straight
Galvanic current density is 75A/m2Under the conditions of be electrolysed 120min, fine copper powder can be deposited on negative electrode；Wherein pure copper anode is
The standard cathode copper of aqueous solution electrolysis refining institute output, titanium sheet negative electrode is TA1；
Step 3, will on step 2 negative electrode deposit fine copper powder remove, clean with pure water 3 times, through 80 DEG C be vacuum dried 2h, obtain
The process that fine copper powder removes is deposited to the dendroid fine copper powder that granularity is 11~20 μm, wherein on negative electrode is：To deposit micro-
After the negative electrode of thin copper powder takes out from electrolytic cell, it is put into pure water quickly, carries out ultrasonic desorption by ultrasonic cleaner, divides
Dissipate, clean, ultrasonic time is 10min.
The dendroid fine copper powder pattern for preparing is dendroid, and copper powder particle size is uniform.Direct current consumption is 3024 (kW
h)·t-1, current efficiency is 84.2%.
Embodiment 7
As shown in figure 1, the method for being somebody's turn to do the electrolytic preparation dendroid fine copper powder in ethanedioic acid, it is comprised the following steps that：
Step 1, in pure water add ethanedioic acid formed concentration for 0.4mol/L ethanedioic acid solution, then according to ethanedioic acid
Ethanedioic acid and the mol ratio of auxiliary reagent are 1 in solution:1 adds auxiliary reagent, and electrolyte is obtained after being well mixed；Wherein aid in
Reagent is 4.70g ammonium chlorides；
Step 2, the 220mL electrolyte for obtaining step 1 are heated to 50 DEG C, are then placed in pure copper anode and titanium sheet negative electrode
In electrolyte, stir speed (S.S.) be 500r/min, control anode and negative electrode area ratio be 1:1st, negative and positive die opening is 50mm, straight
Galvanic current density is 75A/m2Under the conditions of be electrolysed 120min, fine copper powder can be deposited on negative electrode；Wherein pure copper anode is
The standard cathode copper of aqueous solution electrolysis refining institute output, titanium sheet negative electrode is TA1；
Step 3, will on step 2 negative electrode deposit fine copper powder remove, clean with pure water 3 times, through 80 DEG C be vacuum dried 2h, obtain
The process that fine copper powder removes is deposited to the dendroid fine copper powder that granularity is 10~17 μm, wherein on negative electrode is：To deposit micro-
After the negative electrode of thin copper powder takes out from electrolytic cell, it is put into pure water quickly, carries out ultrasonic desorption by ultrasonic cleaner, divides
Dissipate, clean, ultrasonic time is 10min.
The dendroid fine copper powder pattern for preparing is dendroid, and copper powder particle size is uniform.Direct current consumption is 3011 (kW
h)·t-1, current efficiency is 90.2%.
Embodiment 8
As shown in figure 1, the method for being somebody's turn to do the electrolytic preparation dendroid fine copper powder in ethanedioic acid, electricity during rate-determining steps 2
The mixing speed that solution prepares copper powder is 100r/min, and remaining step, condition, parameter are same as Example 4.The fine copper of dendroid
Powder Particle Size is uniform, and particle size range is 12~17 μm.Direct current consumption is 3018 (kWh) t-1, current efficiency is 88.3%.
Embodiment 9
As shown in figure 1, the method for being somebody's turn to do the electrolytic preparation dendroid fine copper powder in ethanedioic acid, electricity during rate-determining steps 2
The mixing speed that solution prepares copper powder is 700r/min, and remaining step, condition, parameter are same as Example 4.The fine copper of dendroid
Powder Particle Size is uniform, and particle size range is 13~20 μm, and pattern is dendroid.Direct current consumption is 3010 (kWh) t-1, electric current effect
Rate is 88.9%.
Embodiment 10
As shown in figure 1, the method for being somebody's turn to do the electrolytic preparation dendroid fine copper powder in ethanedioic acid, electricity during rate-determining steps 2
The DC current flow density that solution prepares copper powder is 50A/m2, remaining step, condition, parameter are same as Example 4.Dendroid is micro-
Thin copper powder particle size is uniform, and particle size range is 11~18 μm, and pattern is dendroid.Direct current consumption is 2984 (kWh) t-1, electric current
Efficiency is 82.9%.
Embodiment 11
As shown in figure 1, the method for being somebody's turn to do the electrolytic preparation dendroid fine copper powder in ethanedioic acid, electricity during rate-determining steps 2
The DC current flow density that solution prepares copper powder is 300A/m2, remaining step, condition, parameter are same as Example 4.Dendroid
Fine copper powder epigranular, particle size range is 12~19 μm, and pattern is dendroid.Direct current consumption is 3112 (kWh) t-1, electricity
Stream efficiency is 90.5%.
Embodiment 12
As shown in figure 1, the method for being somebody's turn to do the electrolytic preparation dendroid fine copper powder in ethanedioic acid, prepares 0.4mol/ in step 1
L ethanedioic acid solution, adds 1.65ml, the ammoniacal liquor auxiliary reagent of mass fraction 25%, and remaining step, condition, parameter are and embodiment
4 is identical.Dendroid fine copper powder epigranular, particle size range is 12~17 μm, and pattern is dendroid.Direct current consumption is 3012
(kW·h)·t-1, current efficiency is 89.5%.
Embodiment 13
As shown in figure 1, the method for being somebody's turn to do the electrolytic preparation dendroid fine copper powder in ethanedioic acid, prepares 0.4mol/ in step 1
L ethanedioic acid solution, adds the ammonium sulfate auxiliary reagent of 11.6g, and remaining step, condition, parameter are same as Example 4.Branch
Shape fine copper powder epigranular, particle size range is 12~19 μm, and pattern is dendroid.Direct current consumption is 3142 (kWh) t-1,
Current efficiency is 87.5%.
Embodiment 14
As shown in figure 1, the method for being somebody's turn to do the electrolytic preparation dendroid fine copper powder in ethanedioic acid, prepares 0.4mol/ in step 1
L ethanedioic acid solution, adds the ammonium hydrogen sulfate auxiliary reagent of 10g, and remaining step, condition, parameter are same as Example 4.Branch
Shape fine copper powder epigranular, particle size range is 11~16 μm, and pattern is dendroid.Direct current consumption is 3187 (kWh) t-1,
Current efficiency is 86.2%.
Specific embodiment of the invention is explained in detail above in association with accompanying drawing, but the present invention be not limited to it is above-mentioned
Implementation method, in the ken that those of ordinary skill in the art possess, can also be before present inventive concept not be departed from
Put that various changes can be made.
Claims (4)
1. a kind of method of the electrolytic preparation dendroid fine copper powder in ethanedioic acid, it is characterised in that comprise the following steps that：
Step 1, in pure water add ethanedioic acid formed concentration be 0.1~0.5mol/L ethanedioic acid solution, then according to second two
Ethanedioic acid and the mol ratio of auxiliary reagent are 1 in acid solution:1 adds auxiliary reagent, and electrolyte is obtained after being well mixed；
Step 2, the electrolyte that step 1 is obtained is heated to 20~50 DEG C, pure copper anode and titanium sheet negative electrode are then placed in electrolysis
It is (1~2) in the area ratio for stirring, controlling anode and negative electrode in liquid:1st, negative and positive die opening is 20~50mm, DC current flow
Density is 50~300A/m2Under the conditions of be electrolysed 30~120min, fine copper powder can be deposited on negative electrode；
Step 3, will on step 2 negative electrode deposit fine copper powder remove, clean with pure water 3 times, through 60~80 DEG C be vacuum dried, obtain
Granularity is 10~20 μm of dendroid fine copper powder；
Auxiliary reagent in wherein described step 1 is one or several in ammoniacal liquor, ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate
Meaning scalemic thereof.
2. according to claim 1 in ethanedioic acid electrolytic preparation dendroid fine copper powder method, it is characterised in that：It is described
Pure copper anode is the standard cathode copper or Cu-CATH-1 of aqueous solution electrolysis refining institute output in step 2.
3. according to claim 1 in ethanedioic acid electrolytic preparation dendroid fine copper powder method, it is characterised in that：It is described
Titanium sheet negative electrode is TA1 or TA2 in step 2.
4. according to claim 1 in ethanedioic acid electrolytic preparation dendroid fine copper powder method, it is characterised in that：It is described
Depositing the process removed of fine copper powder in step 3 on negative electrode is：After the negative electrode for depositing fine copper powder is taken out from electrolytic cell, compared with
It is put into pure water soon, ultrasonic desorption, dispersion, cleaning is carried out by ultrasonic cleaner, ultrasonic time is 10~60min.
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