CN117512698A - Method for preparing high-purity copper through electrolysis under microwave action - Google Patents
Method for preparing high-purity copper through electrolysis under microwave action Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 231
- 239000010949 copper Substances 0.000 title claims abstract description 193
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 191
- 238000000034 method Methods 0.000 title claims abstract description 67
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 51
- 230000009471 action Effects 0.000 title claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 81
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 10
- 230000008021 deposition Effects 0.000 claims abstract description 9
- 239000002608 ionic liquid Substances 0.000 claims description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 108010010803 Gelatin Proteins 0.000 claims description 31
- 239000008273 gelatin Substances 0.000 claims description 31
- 229920000159 gelatin Polymers 0.000 claims description 31
- 235000019322 gelatine Nutrition 0.000 claims description 31
- 235000011852 gelatine desserts Nutrition 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- -1 alkyl methylimidazole chloride Chemical compound 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 10
- 150000001879 copper Chemical class 0.000 claims description 8
- 150000002460 imidazoles Chemical class 0.000 claims description 7
- 238000004070 electrodeposition Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910001200 Ferrotitanium Inorganic materials 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- GOMASLCDQUNHDZ-UHFFFAOYSA-M 1-(3-methylimidazol-3-ium-1-yl)propan-1-amine;chloride Chemical compound [Cl-].CCC(N)[N+]=1C=CN(C)C=1 GOMASLCDQUNHDZ-UHFFFAOYSA-M 0.000 claims 1
- HTZVLLVRJHAJJF-UHFFFAOYSA-M 1-decyl-3-methylimidazolium chloride Chemical compound [Cl-].CCCCCCCCCCN1C=C[N+](C)=C1 HTZVLLVRJHAJJF-UHFFFAOYSA-M 0.000 claims 1
- NKRASMXHSQKLHA-UHFFFAOYSA-M 1-hexyl-3-methylimidazolium chloride Chemical compound [Cl-].CCCCCCN1C=C[N+](C)=C1 NKRASMXHSQKLHA-UHFFFAOYSA-M 0.000 claims 1
- OXFBEEDAZHXDHB-UHFFFAOYSA-M 3-methyl-1-octylimidazolium chloride Chemical compound [Cl-].CCCCCCCCN1C=C[N+](C)=C1 OXFBEEDAZHXDHB-UHFFFAOYSA-M 0.000 claims 1
- 150000004693 imidazolium salts Chemical class 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 21
- 150000002500 ions Chemical class 0.000 abstract description 14
- 238000002360 preparation method Methods 0.000 abstract description 14
- 238000000746 purification Methods 0.000 abstract description 9
- 230000005684 electric field Effects 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 4
- 238000002161 passivation Methods 0.000 abstract description 3
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- 210000001787 dendrite Anatomy 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract description 2
- 230000002452 interceptive effect Effects 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 66
- 239000012535 impurity Substances 0.000 description 52
- 239000007788 liquid Substances 0.000 description 21
- 238000001878 scanning electron micrograph Methods 0.000 description 16
- 229910052719 titanium Inorganic materials 0.000 description 14
- 238000007670 refining Methods 0.000 description 12
- 229910052709 silver Inorganic materials 0.000 description 11
- 238000004506 ultrasonic cleaning Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
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- 239000002253 acid Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 238000010924 continuous production Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000002639 bone cement Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000004857 zone melting Methods 0.000 description 2
- ZDEPXVXEADUOAV-UHFFFAOYSA-N 1-decyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCC[NH+]1CN(C)C=C1 ZDEPXVXEADUOAV-UHFFFAOYSA-N 0.000 description 1
- GPUZITRZAZLGKZ-UHFFFAOYSA-N 1-hexyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCC[NH+]1CN(C)C=C1 GPUZITRZAZLGKZ-UHFFFAOYSA-N 0.000 description 1
- WXJHMNWFWIJJMN-UHFFFAOYSA-N 1-methyl-3-octyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCN1C[NH+](C)C=C1 WXJHMNWFWIJJMN-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- QEKLKJFSTUZMKC-UHFFFAOYSA-N [Cl-].NC(CC)C1=[N+](C=CN1)C Chemical compound [Cl-].NC(CC)C1=[N+](C=CN1)C QEKLKJFSTUZMKC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention relates to a method for preparing high-purity copper by electrolysis under the action of microwaves, belonging to the technical field of electrolytic copper preparation. In the method for preparing high-purity copper by electrolysis, a microwave field is applied in the electrolysis process, and the high-frequency electric field generated by microwaves can enable polar molecules and ions in electrolyte to rotate along with the interactive change of the high-frequency alternating electric field direction, and generate severe collision and friction, so that anode passivation is prevented, the dissolution rate of an anode plate is improved, and the electrolysis efficiency is improved. In addition, the microwave mechanical vibration action can lead the anode slime to be in a suspension state in the electrolyte, and is beneficial to the removal of the anode slime along with the process of electrolyte purification cycle. The copper dendrites on the surface of the cathode copper can be broken by the action of microwave vibration, so that copper grains are thinned. Meanwhile, the phenomenon of concentration polarization of copper ions due to concentration gradient can be avoided, so that the deposition speed of the copper ions on the cathode plate is not uniform, and the surface quality of copper on the cathode plate is improved.
Description
Technical Field
The invention relates to a method for preparing high-purity copper by electrolysis under the action of microwaves, belonging to the technical field of electrolytic copper preparation.
Background
Copper has good ductility, electrical conductivity and thermal conductivity, and is widely applied to the fields of mechanical manufacture, building industry and the like, but because the copper material contains high-content impurities, the copper material is difficult to meet the application in key industries such as high-end equipment manufacture, national defense and military industry and the like. Compared with general copper (4N), high-purity copper (more than or equal to 5N) has more excellent performances, has the advantages of high residual resistivity, high thermal conductivity, low softening temperature and the like, and is widely applied to the high-end technical fields of electronic information, superconducting materials, aerospace and the like.
The preparation method of the high-purity copper mainly comprises electron beam melting, zone melting, electrolytic refining and the like. The zone melting method has the defects of high equipment cost, harsh process conditions and the like, and the electron beam melting method has the problems of difficult control of product quality, high energy consumption, low production efficiency and the like, and the two methods have technical limitations in the aspect of large-scale production. The electrolytic refining method has the advantages of simple process and low cost, and is easy to realize large-scale production. At present, 4N-grade copper is used as a raw material for preparing high-purity copper with 5N-grade or above through one or more times of electrolysis, and electrolyte in an electrolytic tank is continuously discharged from an outlet of the electrolytic tank in the electrolytic process and circularly flows into the electrolytic tank after being subjected to purification treatment by an online purification process so as to realize the purification and circulation treatment of the electrolyte, thereby keeping the impurity content in the electrolyte not to be out of limit. Chinese patent document CN112695346A discloses a process for preparing 6N high-purity copper by one-time electrolysis of a sulfuric acid electrolysis system, and the method disclosed in the patent document is to use 4N-level cathode copper as an anode plate, adopt low-acid low-copper electrolyte, add hydrochloric acid and self-prepared additives for electrolysis to obtain 6N-level high-purity copper. Chinese patent document CN115449848A discloses a preparation method of high-purity copper, wherein the method disclosed in the patent document firstly reduces the Ag content in cathode copper through sulfuric acid system electrolysis, and then reduces S and other impurities in the cathode copper through secondary electrolysis of nitric acid system, and finally obtains 7N-level high-purity copper. Chinese patent document CN107974695B discloses a method for producing ultra-high purity copper by a one-time electrolysis method, wherein 4N-level copper is used as an anode in the method disclosed in the patent document, and a diaphragm is firstly adopted for electrolysis to produce copper sheets; then the copper sheet is used as a cathode and 4N-grade copper is used as an anode for continuous electrolysis, and finally 5N-grade high-purity copper is obtained. However, currently 4N grade copper is produced by fire casting anode plates through one electrorefining. It can be seen that if an anode plate cast from fire refined copper is used as a raw material, the preparation of high-purity copper must undergo more than 2 electrolytic refining processes; if the anode plate cast by adopting the fire refining copper is used for preparing the high-purity copper with more than 5N level by one-time electrolysis, the electrolytic refining preparation process flow of the high-purity copper is greatly shortened, the production efficiency of the high-purity copper is improved, the production cost is reduced, and the application of the high-purity copper in the high-end technical fields of electronic information, superconducting materials, aerospace and the like is promoted.
Therefore, in order to reduce the cost and improve the production efficiency, it is highly demanded to develop a method capable of producing high purity copper by primary electrolytic refining by fire casting an anode plate as a raw material.
Disclosure of Invention
The invention aims to provide a method for preparing high-purity copper by electrolysis under the action of microwaves, which can solve the problems of high cost and low production efficiency when the high-purity copper is prepared by an electrolysis method at present.
In order to achieve the above purpose, the method for preparing high-purity copper by electrolysis under the action of microwaves adopts the following technical scheme:
a method for preparing high-purity copper by electrolysis under the action of microwaves comprises the following steps: providing a cathode, an anode and an electrolyte; immersing the cathode and the anode into electrolyte for electrodeposition, depositing copper on the cathode to form electrolytic copper, and then cleaning and drying the electrolytic copper to obtain high-purity copper; applying a microwave field to the electrolyte during electrodeposition; the electrolyte mainly comprises water, water-soluble copper salt, sulfuric acid, HCl, gelatin and ionic liquid, wherein the ionic liquid is imidazole salt ionic liquid.
In the method for preparing high-purity copper by electrolysis, a microwave field is applied in the electrolysis process, and the high-frequency electric field generated by microwaves can enable polar molecules and ions in electrolyte to rotate along with the interactive change of the high-frequency alternating electric field direction and generate severe collision and friction, and the severe movement and microwave vibration of the polar molecules and ions in the electrolyte can inhibit the adhesion of anode slime on the surface of an anode plate and prevent anode passivation, so that the dissolution rate of the anode plate is improved, and the electrolysis efficiency is improved. In addition, the microwave mechanical vibration action can lead the anode slime to be in a suspension state in the electrolyte, and is beneficial to the removal of the anode slime along with the process of electrolyte purification cycle. The microwave vibration can break up the copper dendrites on the cathode copper surface to prevent the growth of individual grains, so that the copper grains are refined. The invention replaces electric heating by a microwave heating mode, and the heating effect of the microwave heating has the advantages of uniform heating and no hysteresis, so that the ion concentration and the diffusion speed in the electrolyte are more uniform, and the speed of electrochemical reaction and the electrolysis efficiency can be improved; the non-uniform deposition speed of copper ions on the cathode plate caused by concentration polarization phenomenon generated by concentration gradient is avoided, and the surface quality of copper on the cathode is further improved.
The electrolyte adopted in the preparation method of the high-purity copper contains the composite additive consisting of HCl, gelatin and ionic liquid, so that the cathode polarization capability can be improved, the particles on the surface of the cathode are thinned and crystallized densely, the ionic liquid in the electrolyte can carry out complexation reaction with silver ions, and further, the silver ions in the electrolyte are prevented from being discharged and separated out on the cathode, thereby improving the purity of copper on the cathode and the recovery rate of silver and improving the economic benefit. In addition, the addition of the ionic liquid can inhibit the reduction of copper ions at the cathode, so that flat and compact cathode copper is obtained. The composite additive consisting of HCl, gelatin and ionic liquid can be synergistic with microwaves, so that the purity and apparent mass of copper on a cathode are improved.
In order to achieve continuous production, it is preferable that the electrolytic solution is subjected to a purge cycle treatment during electrodeposition.
According to the method for preparing high-purity copper by electrolysis, disclosed by the invention, the electrolyte is subjected to purification and circulation treatment, so that the concentration of floating anode slime and the content of As, sb, bi, ni, co, fe and other impurity ions in the electrolyte can be effectively reduced, gold and silver are prevented from entering a cathode in a mechanical adhesion mode, the quality of cathode copper and the recovery rate of gold and silver are improved, the real-time discharge of anode slime is realized, the problem that the anode slime needs to be periodically cleaned in the traditional copper electrolysis refining preparation method is solved, the continuous production of copper electrolysis is further realized, and the production efficiency is improved. The method for preparing high-purity copper by electrolysis has the advantages of simple process, easy control, high efficiency, low cost, environmental protection and convenient large-scale application.
Preferably, the concentration of copper ions in the electrolyte is 40-50 g/L, the concentration of sulfuric acid is 50-100 g/L, the concentration of HCl is 0.01-0.07 g/L, the concentration of gelatin is 0.07-0.1 g/L, and the concentration of ionic liquid is 0.01-0.045 g/L.
According to the invention, the microwave and the composite additive consisting of HCl, gelatin and ionic liquid play a synergistic effect, so that the anode is prevented from passivation, impurities are prevented from entering cathode copper, the surface crystallization condition of the cathode copper is improved, the content of Ag, S and other impurities in the cathode copper can be obviously reduced, the quality of the cathode copper is improved, the high-purity copper prepared by adopting a pyrogenic casting anode plate as an anode can reach 5N level, the purification effect of more than 2 times of conventional electrolytic refining through one-time electrolysis is realized, and the problems of complicated technological process, low production efficiency and high production cost of the conventional preparation method are effectively solved.
Preferably, the imidazole salt ionic liquid is alkyl methylimidazole chloride and/or aminoalkyl methylimidazole chloride. Preferably, the imidazole salt ionic liquid is C6-C10 alkyl methyl imidazole chloride and/or C3-C5 amino alkyl methyl imidazole chloride. For example, the imidazole salt ionic liquid is selected from one or any combination of 1-hexyl-3-methylimidazole chloride, 1-aminopropyl-3-methylimidazole chloride, 1-octyl-3-methylimidazole chloride and 1-decyl-3-methylimidazole chloride. Compared with other ionic liquids, the ionic liquid has the advantages that the alkyl methylimidazole chloride salt and/or the aminoalkyl methylimidazole chloride salt is selected, so that the content of Ag element, S element and other impurities in high-purity copper formed on the cathode can be greatly and effectively reduced, copper grains formed on the cathode can be finer, and the surface smoothness and compactness of the copper formed on the cathode can be effectively improved.
For cost reduction, preferably, the water-soluble copper salt is copper sulfate and/or a hydrate of copper sulfate.
Preferably, the temperature of the electrolyte is controlled to be 30-40 ℃ during electrolytic deposition. The temperature of the electrolyte is too high, so that the content of free silver ions in the electrolyte is increased, the free silver ions on the surface of cathode copper are separated out, and the content of impurities in the cathode copper is too high; too low a temperature of the electrolyte increases the viscosity of the liquid and the resistance of the electrolyte, reducing the electrolysis efficiency.
In the present invention, applying a microwave field to the electrolyte means continuously applying a microwave field to the electrolyte or intermittently applying a microwave field to the electrolyte.
For better microwave action, the microwave frequency of the microwave field is preferably 2.35-2.65 GHz, and the microwave power density is 5-8W/cm 3 . The excessive power density of the microwaves can lead to gas release in the electrolyte on one hand, to bubble generation or other adverse effects, and to the influence on the uniformity and quality of deposition; on the other hand, the electric field distribution is uneven, resulting in an uneven copper deposit on the cathode.
The method for preparing high-purity copper by electrolysis under the action of microwaves can be implemented by adopting a microwave electrodeposition system disclosed in China patent document CN 115679401A.
Preferably, the cathode is titanium or stainless steel; the anode is copper. Preferably, the mass fraction of copper in the anode is not less than 99%. For example, the anode is fire refined copper or 4N grade copper. For example, the anode is an anode plate or a 4N-grade copper plate cast from fire refined copper.
Preferably, the distance between the cathode and the anode is 20 to 50mm. The distance between the cathode and the anode is controlled within the range, so that not only can the anode slime be prevented from adhering to the surface of the cathode in the sedimentation process, but also the occurrence of interelectrode short circuit can be reduced.
Preferably, direct current is used for electrolytic deposition. Preferably, the current density of the direct current is 150-200A/m 2 . The excessive current density can cause the increase of local current density on the surface of the electrode, so that the electrochemical reaction rate of a part of areas is too high, and the uneven thickness of a deposited copper layer is caused, so that the phenomenon of protrusion or depression occurs; too small a current density may cause a reduction rate of copper ions per unit time to be slow, so that an electrolysis process becomes slow, and production efficiency is lowered.
Preferably, the electrolyte is used in a purifying and circulating treatment mode of upper liquid inlet and lower liquid outlet. The electrolyte is used in a circulating mode of upper liquid inlet and lower liquid outlet, anode slime in the electrolytic tank can be discharged in real time, the electrolyte is purified, the anode slime is prevented from entering a cathode in a mechanical adhesion mode and some impurity ions are prevented from being discharged and separated out at the cathode, and then the purity of high-purity copper is reduced.
Preferably, the method of purification comprises the steps of: filtering the discharged electrolyte, centrifuging the filtered liquid, and then adsorbing the centrifuged liquid; the filtering holes of the filtering material adopted in the filtering process are not more than 0.5 mu m, the rotating speed in the centrifuging process is 600-1200 r/min, the ion exchange resin is adopted in the adsorption treatment process, the average particle size of the ion exchange resin is 5-100 meshes, and the average adsorption capacity is 19.5-25 g/mol. The filtering can remove the large-particle anode slime in the electrolyte, the centrifugation can remove the fine anode slime particles, and the adsorption treatment can further remove impurity ions.
Preferably, the ion exchange resin is an anion exchange resin, which removes a majority of the impurity ions in the electrolyte. The anion exchange resin comprises a silica gel base core and polyethylene polyamine molecules bonded to the surface of the base core through chemical bonds. The anion exchange resin may be commercially available, for example, from the manufacturer Mitsubishi Chemical (Mitsubishi chemical) under the product model Diaion CR11.
The electrolyte is purified, so that the impurity content in the electrolyte can be maintained in a lower range, further continuous production is realized, and in order to ensure that the concentration of the effective components in the electrolyte is maintained in a working concentration range in the electrolysis process, further continuous production is realized, the electrolyte is required to be detected and water, water-soluble copper salt, sulfuric acid, HCl, gelatin or ionic liquid are timely added.
Preferably, the cleaning comprises sequentially carrying out acid washing and ultrasonic cleaning, wherein the washing agent adopted by the acid washing is dilute sulfuric acid, the concentration of the dilute sulfuric acid is 10-20 g/L, the acid washing is to soak electrolytic copper into the dilute sulfuric acid, and the time of the acid washing is 5-10 min; the washing agent adopted by the ultrasonic cleaning is water, the ultrasonic frequency adopted by the ultrasonic cleaning is 20-40 kHz, and the ultrasonic cleaning time is 10-30 min.
Drawings
FIG. 1 is an SEM image of the surface of a high purity copper prepared according to example 2 of the present invention;
FIG. 2 is an SEM image of the surface of a high purity copper prepared according to example 3 of the present invention;
FIG. 3 is an SEM image of the surface of a high purity copper prepared according to comparative example 1 of the present invention;
FIG. 4 is an SEM image of the surface of high purity copper prepared according to comparative example 2 of the present invention;
FIG. 5 is an SEM image of the surface of high purity copper prepared according to comparative example 3 of the present invention;
FIG. 6 is an SEM image of the surface of a high purity copper prepared according to comparative example 4 of the present invention;
FIG. 7 is an SEM image of the surface of high purity copper prepared according to comparative example 5 of the present invention;
fig. 8 is an SEM image of the high purity copper surface prepared in comparative example 6 of the present invention.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
The method for preparing high-purity copper by electrolysis under the action of microwaves in examples 1-4 specifically comprises the following steps:
(1) Adding electrolyte into an electrolytic tank, wherein the electrolytic tank is made of PVC insulating materials and is provided with a liquid inlet, a liquid outlet and a cathode plate placing groove, the cathode plate placing groove is used for placing a cathode plate and an anode plate, the liquid inlet is positioned at the upper end of the electrolytic tank, the liquid outlet is positioned at the lower end of the electrolytic tank, a circulating pipeline is connected between the liquid inlet and the liquid outlet, a circulating pump and a purifying device are arranged on the circulating pipeline, and the purifying device comprises a precision filter, a centrifugal separator and a resin adsorption device which are sequentially connected; a microwave generating device is arranged in the electrolytic tank;
the electrolyte in each example is prepared by mixing water, water-soluble copper salt, sulfuric acid, HCl, gelatin and ionic liquid, wherein the water-soluble copper salt is copper sulfate, the chemical name of the ionic liquid in the electrolyte used in each example, the concentration of copper ions, the concentration of sulfuric acid, the concentration of HCl, the concentration of gelatin and the concentration of the ionic liquid in the electrolyte used in each example are shown in table 1;
(2) Adopting a copper plate as an anode and a titanium plate as a cathode, and then immersing the anode and the cathode into electrolyte; the copper plates and the titanium plates are square, the area of the copper plates is smaller than that of the titanium plates, the copper plates and the titanium plates are alternately placed in parallel in the electrolyte, the center lines of the copper plates and the titanium plates are coincident, and the distance between any adjacent copper plates and titanium plates is x mm; before the copper plate and the titanium plate are used, dilute sulfuric acid solution is used for soaking to remove surface stains, and a polisher is used for polishing to clean impurities remained on the surfaces of the copper plate and the titanium plate and enable the roughness of the surfaces of the titanium plate to be less than 30nm, so that the phenomenon that the deposition of copper on a cathode plate is affected due to the fact that the impurities remained on a cathode plate and an anode plate are introduced into electrolyte is avoided, and the quality of the prepared high-purity copper is reduced; the type and composition (including the mass fraction of copper element and the type and content of each impurity) of the copper plate used in each example are shown in table 2; the number of copper plates, the number of titanium plates, and the distance between any adjacent copper plate and titanium plate used in each example are shown in table 3;
(3) Controlling the temperature of the electrolyte at T ℃, starting a circulating pump on a circulating pipeline to enable the electrolyte in the electrolytic tank to be in a purifying and circulating state, then starting a direct current power supply connected to a cathode and an anode, and simultaneously starting a microwave generating device to apply a microwave field to the electrolyte in the electrolytic tank, wherein the frequency of the microwave is controlled to be y GHz, and the power density of the microwave is j W/cm 3 The direct current density on the cathode and anode was p A/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Copper ions in the electrolyte are continuously deposited on the cathode to form electrolytic copper, the electrolytic copper in a block shape is periodically taken off from the cathode, and then the taken-off electrolytic copper is sequentially subjected to acid washing (dilute sulfuric acid is adopted for acid washing) and ultrasonic cleaning (water is adopted as a detergent for ultrasonic cleaning, m kHz is adopted as ultrasonic frequency for ultrasonic cleaning, and t is adopted as time for ultrasonic cleaning) 1 min), drying the electrolytic copper after ultrasonic cleaning to constant weight to obtain high-purity copper, and then vacuum packaging the high-purity copper.
In the electrolytic process, the copper plate at the anode is continuously dissolved into electrolyte to cause the composition of the electrolyte to be changed, in order to ensure that impurities in the electrolyte are not enriched and further maintain continuous production, in the electrolytic copper production process, the electrolyte in the electrolytic tank is discharged from a liquid outlet of the electrolytic tank and is purified by a purifying device on a circulating pipeline and then recycled to a liquid inlet of the electrolytic tank to realize recycling of the electrolyte, during the purifying process, a filter hole of a filter material in a precision filter is 0.05 mu m, the rotating speed of a centrifugal separator is q r/min, an anion exchange resin is placed in a resin adsorption device, the particle size of the anion exchange resin is 5-100 meshes, the average adsorption capacity is m g/mol, the anion exchange resin comprises a silica gel base core and polyethylene polyamine molecules bonded on the surface of the base core through chemical bonds, and the manufacturer of the anion exchange resin is Mitsubishi Chemical (Mitsubishi chemical) company, and the product model number of Diaion CR11;
the method of the purification treatment comprises the following steps: filtering electrolyte discharged from a liquid outlet of the electrolytic tank by a precision filter, and then introducing the filtered liquid into a centrifugal separator for centrifugal treatment, wherein the centrifugal time is t 2 min, centrifuging to remove suspended anode slime with particle size larger than 0.5 μm and insoluble large particles in the filtered liquid, introducing the centrifuged liquid into a resin adsorption device for adsorption treatment, wherein the adsorption treatment can remove impurity ions (such as impurity ions of iron, zinc, nickel, lead and the like) in the centrifuged liquid, so as to ensure that the impurity content of the electrolyte in the electrolytic tank is controlled in a lower range, and the mass fraction of main impurity elements in the adsorbed liquid needs to meet the following conditions: iron ions < 1.0g/L, zinc ions < 0.5g/L, nickel ions < 1.0g/L, lead ions < 0.2g/L, and the concentrations of the other impurity ions (Ag, S, sb, bi, co, as, si and Sn) are all less than 0.2g/L;
in order to avoid the change of the concentration of the effective components in the electrolyte and further influence continuous production, the concentration change rate of the water-soluble copper salt, sulfuric acid, HCl, gelatin and the ionic liquid in the electrolyte needs to be detected and controlled to be not more than 1%;
the process parameters (electrolyte temperature T, microwave frequency y, microwave power density j, DC current density p on cathode and anode, ultrasonic frequency m for ultrasonic cleaning, ultrasonic cleaning time T) during electrolysis in each example 1 The rotational speed q of the centrifuge and the average adsorption capacity r) of the anion exchange resin are shown in table 4.
In various embodiments, the method of applying a microwave field to the electrolyte in the electrolytic cell is as follows: in examples 1-4, a microwave field was continuously applied to the electrolyte in the electrolytic cell.
Table 1 chemical names of ionic liquids in the electrolytes used in the examples, concentrations of copper ions, sulfuric acid concentration, HCl concentration, gelatin concentration, and ionic liquid concentration in the electrolytes used in the examples
Table 2 chemical composition of copper plate used in each example
TABLE 3 number of copper plates, number of titanium plates, and distance between any adjacent copper plates and titanium plates used in each example
| Preparation method | Number of copper plates | Number of titanium plates | x |
| Example 1 | 1 | 2 | 50 |
| Example 2 | 1 | 2 | 40 |
| Example 3 | 2 | 3 | 20 |
| Example 4 | 3 | 4 | 30 |
TABLE 4 Process parameters at the time of electrolysis in the examples
| Preparation method | T | y | j | p | m | t 1 | q | r |
| Example 1 | 30 | 2.35 | 5 | 185 | 20 | 10 | 900 | 19.5 |
| Example 2 | 35 | 2.45 | 8 | 200 | 30 | 20 | 1000 | 25 |
| Example 3 | 40 | 2.65 | 7 | 150 | 30 | 30 | 1200 | 22 |
| Example 4 | 38 | 2.55 | 6 | 160 | 40 | 15 | 600 | 21 |
Comparative example 1
The method for electrolytically preparing high purity copper of this comparative example differs from the method for electrolytically preparing high purity copper under the action of microwaves of example 2 only in that the microwave generating device is not turned on, i.e., no microwave field is applied, in the preparation process of this comparative example.
Comparative example 2
The method for preparing high-purity copper by electrolysis under the action of microwaves of this comparative example is different from the method for preparing high-purity copper by electrolysis under the action of microwaves of example 2 only in that the mass fractions of HCl, gelatin and ionic liquid in the electrolyte used in this comparative example are all 0.
Comparative example 3
The method of electrolytically preparing high purity copper under the action of microwaves of this comparative example is different from the method of electrolytically preparing high purity copper under the action of microwaves of example 2 only in that gelatin is replaced with bone glue in the electrolyte used in this comparative example.
Comparative example 4
The method for electrolytically preparing high purity copper under microwave in this comparative example is different from the method for electrolytically preparing high purity copper under microwave in example 2 only in that the mass fraction of HCl in the electrolyte used in this comparative example is 0 and the sum of the mass fractions of gelatin and ionic liquid is 150×10 -3 g/L, and the mass ratio of the gelatin to the ionic liquid is 90:35.
Comparative example 5
The method for electrolytically preparing high purity copper under microwave in this comparative example is different from the method for electrolytically preparing high purity copper under microwave in example 2 only in that the mass fraction of gelatin in the electrolyte used in this comparative example is 0 and the sum of the mass fractions of HCl and ionic liquid is 150×10 -3 g/L, and the mass ratio of HCl to ionic liquid is 25:35.
Comparative example 6
The method for preparing high purity copper by electrolysis under microwave action of the present comparative example is different from the method for preparing high purity copper by electrolysis under microwave action of example 2 only in that the mass fraction of the ionic liquid in the electrolyte used in the present comparative example is 0 and the sum of the mass fractions of HCl and gelatin is 150×10 -3 g/L, and the mass ratio of HCl to gelatin is 25:90.
Experimental example 1
To examine the quality of the high purity copper prepared in examples 1 to 4 and comparative examples 1 to 6, the type and content of impurity elements in the high purity copper prepared in each example and comparative example were tested by glow discharge mass spectrometry, and the type and content of a part of impurity elements are shown in Table 5, and the content of other impurity elements not shown meets the impurity element content requirements in the national standard of high purity copper (GB/T26017-2020). The total content of impurity elements in the high purity copper prepared in each of examples and comparative examples and the content of copper element are shown in tables 6 to 7.
TABLE 5 types and contents of part of impurity elements in high purity copper prepared in examples and comparative examples
| Preparation method | Ag | S | Sb | Ni | Bi | Co | Fe | As | Si | Pb | Sn |
| Example 1 | 0.8 | 1.6 | 0.14 | 0.37 | 0.07 | 0.39 | 0.29 | 0.13 | 0.36 | 0.08 | 0.12 |
| Example 2 | 0.5 | 1.5 | 0.12 | 0.42 | 0.05 | 0.36 | 0.26 | 0.11 | 0.34 | 0.05 | 0.16 |
| Example 3 | 0.1 | 0.45 | 0.01 | 0.01 | 0.01 | 0.01 | 0.04 | 0.04 | 0.05 | 0.02 | 0.01 |
| Example 4 | 0.2 | 0.36 | 0.01 | 0.01 | 0.01 | 0.01 | 0.07 | 0.03 | 0.03 | 0.01 | 0.01 |
| Comparative example 1 | 5.5 | 6.3 | 2.6 | 0.75 | 0.91 | 1.5 | 2.4 | 1.4 | 0.78 | 1.6 | 0.48 |
| Comparative example 2 | 3.7 | 5 | 2.8 | 0.92 | 1.3 | 1.7 | 3.1 | 1.9 | 0.69 | 1.4 | 0.66 |
| Comparative example 3 | 2.4 | 2.3 | 1.2 | 0.58 | 0.85 | 1.4 | 1.8 | 0.62 | 0.52 | 0.44 | 0.65 |
| Comparative example 4 | 2.6 | 2.5 | 1.3 | 0.54 | 0.81 | 1.6 | 2.1 | 0.75 | 0.72 | 0.35 | 0.63 |
| Comparative example 5 | 3.1 | 2.6 | 1.2 | 0.49 | 0.65 | 1.5 | 1.7 | 0.74 | 0.65 | 0.63 | 0.72 |
| Comparative example 6 | 2.9 | 2.8 | 1.5 | 0.63 | 0.74 | 1.3 | 1.5 | 0.83 | 0.67 | 0.64 | 0.82 |
TABLE 6 Total content (ppm) of impurity elements and copper content (wt%) in high purity copper prepared in examples 1 to 4
| Type(s) | Example 1 | Example 2 | Example 3 | Example 4 |
| Total amount of impurities | 4.35 | 3.87 | 0.75 | 0.75 |
| Copper (Cu) | ＞99.999 | ＞99.999 | ＞99.9999 | ＞99.9999 |
TABLE 7 Total content (ppm) of impurity elements and copper content (wt%) in high purity copper prepared in comparative examples 1 to 6
| Type(s) | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Total amount of impurities | 26.88 | 26.26 | 10.38 | 12.43 | 11.34 | 14.33 |
| Copper (Cu) | ＜99.999 | ＜99.999 | ＜99.999 | ＜99.999 | ＜99.999 | ＜99.999 |
As is clear from tables 5 to 7, the impurity element content of Ag, S, ni, co, fe, si and the like in the high-purity copper produced by using the fire refining cast anode plate as the raw material in examples 1 to 2 is far lower than the impurity element content of 5N-grade high-purity copper specified in the national standard (GB/T26017-2020), and the impurity element content of Ag, S, ni, co, fe, si and the like in the high-purity copper produced by using the 4N-grade copper produced by the electrolytic refining as the raw material in examples 3 to 4 is far lower than the impurity element content of 6N-grade high-purity copper specified in the national standard (GB/T26017-2020). Therefore, compared with the traditional method for preparing the high-purity copper by adopting repeated electrolytic refining, the preparation method provided by the invention not only can shorten the production flow of the high-purity copper and improve the production efficiency of the high-purity copper, but also has the advantages of saving electric energy and reducing the production cost of the high-purity copper by the synergistic effect of microwaves and electrolyte.
The experiments of comparative examples 1 to 5, which were carried out on the basis of example 2, show that the Ag content in the cathode copper prepared in example 2 was 0.5ppm, and the Ag content in the cathode copper prepared in comparative example 1 was 5.5ppm, thus, compared with the Ag content in the cathode copper prepared in comparative example 1, the Ag content in the cathode copper prepared in example 2 was reduced by 90.91%, and the impurity element content such as Sb, as, pb, S was also reduced, indicating that the microwave can effectively reduce the content of the impurity element such as silver in the cathode copper.
Comparative example 2 is an experiment in which no composite additive (consisting of HCl, gelatin, and ionic liquid) was added, and the Ag content in the prepared cathode copper was 3.7ppm; therefore, the content of Ag in the cathode copper prepared in example 2 was reduced by 86.49% and the content of impurity elements such as Sb, as, pb, S was also reduced, compared to comparative example 1, indicating that the composite additive can effectively reduce the content of impurity elements such as silver in the cathode copper.
Comparative example 3 is an experiment in which gelatin was replaced with bone glue, and the Ag content in the prepared cathode copper was 2.4ppm, so that the Ag content in the cathode copper prepared in example 2 was reduced by 79.12% and the contents of impurity elements such As Sb, as, pb were also reduced, indicating that gelatin As an additive component has a better effect of reducing the impurity element content than bone glue for the electrolyte system of the present invention.
Comparative example 4 is an experiment using only gelatin and ionic liquid, and the Ag content in the prepared cathode copper is 2.6ppm, so that the Ag content in the cathode copper prepared in example 2 is reduced by 80.77% and the contents of impurity elements such As Sb, as, pb, etc. are also reduced, indicating that HCl can act synergistically with gelatin and ionic liquid to further reduce the contents of impurity elements for the electrolyte system of the present invention.
Comparative example 5 is an experiment using only HCl and ionic liquid, and the Ag content in the prepared cathode copper is 3.1ppm, so that the Ag content in the cathode copper prepared in example 2 is reduced by 83.87% and the contents of impurity elements such As Sb, as, pb, etc. are also reduced, indicating that gelatin can act synergistically with HCl and ionic liquid to further reduce the contents of impurity elements for the electrolyte system of the present invention.
Comparative example 6 is an experiment using only HCl and gelatin, and the Ag content of the prepared cathode copper is 2.9ppm, so that the Ag content of the prepared cathode copper is reduced by 82.76% compared with that of comparative example 6, and the contents of impurity elements such As Sb, as, pb and the like in the prepared cathode copper are all higher than those of the prepared cathode copper of example 2, which indicates that for the electrolyte system of the present invention, the ionic liquid can synergistically act with HCl and gelatin, and further reduce the impurity element content.
In conclusion, the microwave effect can reduce the silver content in the cathode copper and the content of harmful impurity elements; HCl, gelatin and ionic liquid can play a synergistic role, so that the contents of Ag and S and the contents of harmful impurity elements in cathode copper are reduced; the ion exchange resin has the function of reducing the impurity ion content in the copper electrolysis process, and can improve the quality of high-purity copper; the synergistic effect of the microwave, the composite additive and the ion exchange resin has obvious effect of improving the quality of cathode copper.
Experimental example 2
To examine the surface morphology of the high purity copper prepared in each of the examples and comparative examples, the surface of the high purity copper prepared in each of the examples and comparative examples was characterized using a scanning electron microscope. SEM images of the high-purity copper surfaces prepared in example 2 and 3 are shown in fig. 1 and 2, and SEM images of the high-purity copper surfaces prepared in comparative examples 1 to 6 are shown in fig. 3 to 8, respectively.
As can be seen from fig. 1-2, the surface copper of the high-purity copper prepared in example 2 has fine copper grains and a relatively flat surface; the surface copper grains of the high-purity copper prepared in the example 3 are fine, and the surface is even and smooth;
as shown in the SEM image of the surface of the high-purity copper prepared in comparative example 1 as shown in FIG. 3, as can be seen from FIG. 3, the surface of the high-purity copper prepared in comparative example 1 is rough, the copper crystal grains are highly disordered, and the surface morphology of the cathode copper prepared in example 2 is compared with that of the cathode copper prepared in example 2, microwaves can enable the surface of the copper to be smooth and compact, and the apparent quality of the copper is improved.
As shown in FIG. 4, the SEM image of the high purity copper surface prepared in comparative example 2 shows that the high purity copper surface prepared in comparative example 2 is dense but has obvious coarse grains, and the comparison of the surface morphology of cathode copper in example 2 shows that the composite additive composed of HCl, gelatin and ionic liquid has the functions of refining copper grains and enabling copper grains to be deposited uniformly.
The SEM image of the surface of the high-purity copper prepared in comparative example 3 is shown in fig. 5, and as can be seen from fig. 5, the surface of the high-purity copper prepared in comparative example 3 has obvious gaps among copper grains, has poor flatness, and compared with the surface morphology of the cathode copper in example 2, the gelatin has better effect of improving the uniformity of the surface of the plating layer and the flatness of the grains.
The SEM image of the surface of the high-purity copper prepared in comparative example 4 is shown in fig. 6, and as can be seen from fig. 6, the surface of the high-purity copper prepared in comparative example 4 is rough, copper particles are obvious, and comparison with the surface morphology of the cathode copper in example 2 shows that HCl has better effect on improving the deposition rate and grain growth of copper grains.
As shown in FIG. 7, the SEM image of the surface of the high purity copper prepared in comparative example 5 shows that the copper grains on the surface of the high purity copper prepared in comparative example 5 are not uniformly grown, and have obvious large particles, and compared with the morphology of the cathode copper in example 2, the gelatin has the effects of uniformly growing copper grains on the surface of the high purity copper and ensuring fine crystallization.
As shown in the SEM image of the surface of the high-purity copper prepared in comparative example 6 as shown in FIG. 8, as can be seen from FIG. 8, although the surface of the high-purity copper prepared in comparative example 6 has fine crystal grains and compact crystals, the surface of the high-purity copper has obvious impurity particles, and the surface morphology comparison with the cathode copper in example 2 shows that the ionic liquid can reduce the adhesion of impurity ions and fine particles on the surface of the high-purity copper and improve the apparent quality of copper.
Claims (10)
1. The method for preparing the high-purity copper by electrolysis under the action of microwaves is characterized by comprising the following steps of: providing a cathode, an anode and an electrolyte; immersing the cathode and the anode into electrolyte for electrodeposition, depositing copper on the cathode to form electrolytic copper, and then cleaning and drying the electrolytic copper to obtain high-purity copper; applying a microwave field to the electrolyte during electrodeposition; the electrolyte mainly comprises water, water-soluble copper salt, sulfuric acid, HCl, gelatin and ionic liquid, wherein the ionic liquid is imidazole salt ionic liquid.
2. The method for preparing high-purity copper by electrolysis under the action of microwaves according to claim 1, wherein the concentration of copper ions in the electrolyte is 40-50 g/L, the concentration of sulfuric acid is 50-100 g/L, the concentration of HCl is 0.01-0.07 g/L, the concentration of gelatin is 0.07-0.1 g/L, and the concentration of ionic liquid is 0.01-0.045 g/L.
3. The method for preparing high-purity copper by electrolysis under the action of microwaves according to claim 1, wherein the imidazole salt ionic liquid is alkyl methylimidazole chloride and/or aminoalkyl methylimidazole chloride.
4. The method for preparing high-purity copper by electrolysis under the action of microwaves according to claim 3, wherein the imidazole salt ionic liquid is C6-C10 alkyl methylimidazole chloride and/or C3-C5 aminoalkyl methylimidazole chloride.
5. The method for preparing high-purity copper by electrolysis under the action of microwaves according to claim 4, wherein the imidazolium salt ionic liquid is one or any combination of 1-hexyl-3-methylimidazolium chloride, 1-aminopropyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium chloride and 1-decyl-3-methylimidazolium chloride.
6. The method for the electrolytic production of high purity copper under the action of microwaves according to one of claims 1 to 5, wherein the water-soluble copper salt is copper sulfate and/or a hydrate of copper sulfate.
7. The method for producing high purity copper by electrolysis under the action of microwave according to any one of claims 1 to 5, wherein the microwave field has a microwave frequency of 2.35 to 2.65GHz and a microwave power density of 5 to 8W/cm 3 。
8. The method for producing high purity copper by electrolysis under the action of microwave according to any one of claims 1 to 5, wherein the temperature of the electrolytic solution is controlled to be 30 to 40 ℃ during the electrolytic deposition.
9. The method for producing high purity copper by electrolysis under the action of microwaves according to any one of claims 1 to 5, wherein the distance between the cathode and the anode is 20 to 50mm.
10. The method for preparing high-purity copper by electrolysis under the action of microwave according to any one of claims 1 to 5, wherein direct current is used in the electrolytic deposition, and the current density of the direct current is 150 to 200A/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The cathode is titanium or stainless steel.
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