CN115386921A - Copper dissolving method for electrolytic copper foil - Google Patents
Copper dissolving method for electrolytic copper foil Download PDFInfo
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- CN115386921A CN115386921A CN202211173834.3A CN202211173834A CN115386921A CN 115386921 A CN115386921 A CN 115386921A CN 202211173834 A CN202211173834 A CN 202211173834A CN 115386921 A CN115386921 A CN 115386921A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 210
- 239000010949 copper Substances 0.000 title claims abstract description 183
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 179
- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000011889 copper foil Substances 0.000 title claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 113
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 59
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- -1 iron ions Chemical class 0.000 claims abstract description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052742 iron Inorganic materials 0.000 claims abstract description 32
- 239000000126 substance Substances 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 29
- 238000007747 plating Methods 0.000 claims description 23
- 230000002378 acidificating effect Effects 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 3
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 3
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 20
- 239000013589 supplement Substances 0.000 abstract description 12
- 239000000047 product Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 30
- 239000008151 electrolyte solution Substances 0.000 description 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 7
- 229910001447 ferric ion Inorganic materials 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 239000005751 Copper oxide Substances 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 229910000431 copper oxide Inorganic materials 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000006259 organic additive Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- 238000011978 dissolution method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000011083 sodium citrates Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
Abstract
The application provides a copper dissolving method of an electrolytic copper foil, which comprises the following steps: providing a copper dissolving tank filled with metal copper; introducing a first electrolyte containing iron ions into a copper dissolving tank to dissolve at least part of the surface of metal copper to obtain a reaction solution containing copper ions and ferrous ions; introducing the reaction solution into an electrolytic bath to supplement copper ions and ferrous ions into the first electrolyte to obtain a second electrolyte; carrying out electrolytic reaction on the second electrolyte so as to ensure that copper ions and ferrous ions are reduced into copper simple substances and oxidized into iron ions respectively to obtain a third electrolyte; and introducing the third electrolyte into the copper dissolving tank to continuously dissolve at least part of the surface of the metal copper. The electrolytic copper foil copper dissolving method provided by the application has the advantages of simple process and lower cost, and is beneficial to improving the stability of the quality of an electroplated product.
Description
Technical Field
The application relates to the technical field of electrolytic copper foil, in particular to a copper dissolving method of electrolytic copper foil.
Background
At present, electrolytic copper foil and electrolytic composite copper foil are mainly prepared by an electroplating deposition method, generally, copper ions in a plating solution obtain electrons under the condition of switching on a power supply negative electrode, the electrons are reduced into a copper simple substance, and then the copper simple substance is deposited on a proper carrier (including a cathode roller or a seed layer after physical deposition). The copper dissolving process is the first process of electrolytic copper foil production, and aims to put metal copper into a sulfuric acid solution to be dissolved into a copper sulfate solution, and supplement the copper sulfate solution into a plating solution so as to supply the copper foil to the subsequent copper foil production process. In the conventional copper dissolution method, the copper ions in the plating solution are generally from the following sources: (1) Dissolving the copper oxide auxiliary tank, and supplementing copper ions into the plating solution; (2) Under the action of air and sulfuric acid, a copper raw material is dissolved in a copper dissolving tank and then is introduced into plating solution; (3) The phosphorus copper ball is used as a soluble anode, and is slowly dissolved into the plating solution after being electrified. Although the above-mentioned conventional copper dissolving methods can supplement copper ions in the plating solution, the methods still have the disadvantages of high cost, complicated process, and unstable quality of the obtained plated product.
Disclosure of Invention
Based on the above, the present application provides a copper dissolving method for electrolytic copper foil, which aims to improve the stability of the quality of the electroplated product and reduce the cost and complexity of the copper dissolving process.
The application provides a copper dissolving method of an electrolytic copper foil, which comprises the following steps:
providing a copper dissolving tank filled with metal copper;
introducing a first electrolyte containing iron ions into the copper dissolving tank to dissolve at least part of the surface of the metal copper to obtain a reaction solution containing the copper ions and ferrous ions;
introducing the reaction solution into an electrolytic bath to supplement copper ions and ferrous ions into the first electrolyte to obtain a second electrolyte;
carrying out electrolytic reaction on the second electrolyte so as to ensure that the copper ions and the ferrous ions are respectively reduced into copper simple substances and oxidized into iron ions, thereby obtaining a third electrolyte; and
and introducing the third electrolyte into the copper dissolving tank to continuously dissolve at least part of the surface of the metal copper.
According to any embodiment of the present application, the concentrations of iron ions in the first electrolyte, the second electrolyte, and the third electrolyte are each independently 0.2g/L to 20g/L.
According to any embodiment of the present application, the concentrations of iron ions in the first electrolyte, the second electrolyte, and the third electrolyte are each independently 6g/L to 8g/L.
According to any embodiment of the present application, the first electrolyte solution, the second electrolyte solution, and the third electrolyte solution further each independently contain ferrous ions and copper ions, wherein the ferrous ions are each independently at a concentration of 0.1g/L to 25g/L.
According to any embodiment of the present application, the concentration of ferrous ions is from 2g/L to 25g/L.
According to any embodiment of the present application, the concentration of copper ions is 40g/L to 100g/L.
In accordance with any embodiment of the present application, the first electrolyte, the second electrolyte, and the third electrolyte further each independently comprise one or more of sulfuric acid, chloride ions, and an acidic copper plating additive.
According to any embodiment of the application, the concentration of the sulfuric acid is from 80g/L to 250g/L.
According to any embodiment of the present application, the concentration of chloride ions is each independently from 5ppm to 100ppm.
In accordance with any embodiment of the present application, the acidic copper plating additive includes one or more of a complexing agent, an accelerator, and an inhibitor; optionally, the complexing agent comprises at least one of potassium sodium tartrate, sodium citrate, disodium ethylenediaminetetraacetate, and triethanolamine; optionally the accelerator comprises at least one of sodium polydithio dipropyl sulfonate and sodium 3-mercapto-1-propane sulfonate; optionally the inhibitor comprises polyethylene glycol.
In the copper dissolving method of electrolytic copper foil provided by the application, firstly, a copper dissolving tank filled with metal copper is provided, then a first electrolyte containing iron ions is introduced into the copper dissolving tank, the iron ions can be used as an oxidant to oxidize and dissolve the surface of the metal copper, so that a reaction liquid containing the copper ions and ferrous ions is generated, then the reaction liquid is introduced into the electrolytic tank, and then the copper ions and the ferrous ions can be supplemented into the first electrolyte to obtain a second electrolyte. The second electrolyte can perform an electrolytic reaction in an electrolytic tank, copper ions in the second electrolyte can be reduced into a copper simple substance in the electrolytic reaction, and then the copper simple substance is continuously deposited on the carrier to obtain the copper foil; the ferrous ions are oxidized into ferric ions, so that a third electrolyte containing the ferric ions is formed, and the third electrolyte is introduced into the copper dissolving tank again in the subsequent process to continuously dissolve the metal copper. Therefore, the method can be continuously circulated between the copper dissolving tank and the electrolytic tank, and realizes the continuous replenishment of copper ions in the circulating process, and finally the copper foil is obtained. The method has simple process, does not need heating and air filling in the process, does not need facilities such as equipment, pipelines and the like required by a conventional copper dissolving tank, does not need copper oxide with higher price after the method is used, and does not generate anode mud and particles, thereby being beneficial to improving the stability of the quality of the electroplated product.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments or the conventional technologies of the present application, the drawings used in the description of the embodiments or the conventional technologies will be briefly introduced below, it is obvious that the drawings in the description below are only the embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to the disclosed drawings without creative efforts.
Fig. 1 is a schematic plan view of an apparatus used in a copper dissolution method according to an embodiment of the present application.
Description of reference numerals:
1: an electrolytic cell; 2: a copper dissolving tank filled with metal copper; 3: a pipeline; 4: a pipeline;
11: an anode; 12: a cathode; 21: metallic copper.
Detailed Description
To facilitate an understanding of the present application, the present application will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present application are given in the accompanying drawings. This application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual numerical value between the endpoints of a range is encompassed within that range. Thus, each point or individual value can form a range not explicitly recited as its own lower or upper limit in combination with any other point or individual value or in combination with other lower or upper limits.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. It is noted that, as used herein, unless otherwise indicated, the term "and/or" includes any and all combinations of one or more of the associated listed items, and the terms "above", "below" are intended to include the present numbers, with the meaning of "more than one" of "one or more" being two or more.
In this application, unless expressly stated or limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly and encompass, for example, both fixed and removable connections or integral parts thereof; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be interconnected within two elements or in a relationship where two elements interact with each other unless otherwise specifically limited. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art as appropriate.
It will be understood that when an element is referred to as being "secured to" or "disposed on" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "upper," "lower," "left," "right," and the like as used herein are for illustrative purposes only and do not denote a unique embodiment.
The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. At various points throughout this application, guidance is provided through a list of embodiments that can be used in various combinations. In each instance, the list is merely a representative group and should not be construed as exhaustive.
In the current process of electrolytic copper foil and electrolytic composite copper foil, the traditional copper dissolving method generally comprises the following steps: (1) Dissolving the copper oxide auxiliary tank, and supplementing copper ions into the plating solution; (2) Under the action of air and sulfuric acid, a copper raw material is dissolved in a copper dissolving tank and then is introduced into plating solution; (3) Phosphorus copper balls are used as a soluble anode, and are slowly dissolved into the plating solution after being electrified. The inventor finds that in the process of research, in the method (1), the cost is high because the copper oxide needs to be prepared from pure copper through a process; in the method (2), the copper dissolving tank has complex working procedures, heating and gas filling are needed in the process, the requirements on equipment, pipelines and filtering precision are high, the bottom copper protecting amount is high, and the loss of plating solution additives is high; in the method (3), anode mud is generated when the phosphorus copper balls are used, the anode mud needs to be maintained and cleaned regularly, and the copper balls cannot be used again and need to be replaced after being too small, so that the waste of the copper balls and the cost of manpower and material resources are increased.
In order to solve the foregoing technical problems, the inventors propose the following technical solutions.
The embodiment of the application provides a copper dissolving method of an electrolytic copper foil, which comprises the following steps:
s10, providing a copper dissolving tank filled with metal copper;
s20, introducing a first electrolyte containing iron ions into the copper dissolving tank to dissolve at least part of the surface of the metal copper to obtain a reaction liquid containing the copper ions and ferrous ions;
s30, introducing the reaction solution into an electrolytic cell to supplement copper ions and ferrous ions into the first electrolyte to obtain a second electrolyte;
s40, carrying out an electrolytic reaction on the second electrolyte so that the copper ions and the ferrous ions are reduced into copper simple substances and oxidized into iron ions respectively to obtain a third electrolyte;
s50, introducing the third electrolyte into the copper dissolving tank to continuously dissolve at least part of the surface of the metal copper.
In the copper dissolving method of electrolytic copper foil provided by the application, firstly, a copper dissolving tank filled with metal copper is provided, then a first electrolyte containing iron ions is introduced into the copper dissolving tank, the iron ions can be used as an oxidant to oxidize and dissolve the surface of the metal copper, so that a reaction liquid containing the copper ions and ferrous ions is generated, then the reaction liquid is introduced into the electrolytic tank, and then the copper ions and the ferrous ions can be supplemented into the first electrolyte to obtain a second electrolyte. The second electrolyte can perform an electrolytic reaction in an electrolytic tank, copper ions in the second electrolyte can be reduced into a copper simple substance in the electrolytic reaction, and then the copper simple substance is continuously deposited on the carrier to obtain the copper foil; the ferrous ions are oxidized into ferric ions, so that a third electrolyte containing the ferric ions is formed, and the third electrolyte is introduced into the copper dissolving tank again in the subsequent process to continuously dissolve the metal copper. The method can continuously circulate between the copper dissolving tank and the electrolytic tank, realize the continuous replenishment of copper ions in the circulating process, and finally obtain the copper foil. The method has simple process, does not need heating and air filling in the process, does not need facilities such as equipment, pipelines and the like required by a conventional copper dissolving tank, does not need copper oxide with higher price after the method is used, and does not generate anode mud and particles, thereby being beneficial to improving the stability of the quality of the electroplated product.
In some embodiments, as shown in fig. 1, which is a schematic plan view of an apparatus used in the above copper dissolving method of the present application, the apparatus includes an electrolytic bath 1 and a copper dissolving bath 2, the copper dissolving bath 2 and the electrolytic bath 1 are both provided with openings, and the openings are connected through a pipeline 3 and a pipeline 4, so that the copper dissolving bath 2 and the electrolytic bath 1 can be communicated through a pipeline. The electrolytic bath 1 comprises an anode 11, a cathode 12 and an electrolyte, and the copper dissolving bath 2 comprises metal copper 21.
When the copper foil electrolysis and copper dissolution processes from step S10 to step S50 are performed in the above apparatus, the first electrolyte in the electrolytic cell 1 is first introduced into the copper dissolution tank 2 through the pipeline 3, and since the first electrolyte contains iron ions and ferrous ions, the redox reaction in the following formula (1) occurs in the copper dissolution tank:
2Fe 3+ +Cu→2Fe 2+ +Cu 2+ (1)
at least part of the surface of the metal copper in the copper dissolving tank is dissolved into copper ions through the reaction in the formula (1), and simultaneously iron ions in the first electrolyte are reduced into ferrous ions, so that a reaction liquid containing the copper ions and the ferrous ions is generated; and introducing the obtained reaction solution into the electrolytic tank 1 from the copper dissolving tank 2 through the pipeline 2, so that copper ions and ferrous ions can be supplemented into the first electrolyte to obtain a second electrolyte. The copper ions and the ferrous ions returned to the second electrolytic solution undergo reduction reactions and oxidation reactions in the cathode 12 and the anode 11 as shown in the following formulas (2) to (3) and formulas (4) to (5), respectively:
Cu 2+ +2e→Cu (2) Fe 3+ +e→Fe 2+ (3)
Fe 2+ -e→Fe 3+ (4) 2H 2 O–4e→4H + +O 2 ↑ (5)
as can be seen from the above reaction formulas (2) to (3), after the cathode 12 undergoes the reduction reaction, the copper ions in the second electrolyte are reduced to elemental copper, and along with the progress of the electrolysis reaction, the copper dissolution tank 2 can continuously supplement the copper ions for the electrolysis reaction, and the copper ions will also be continuously reduced to elemental copper and deposited on the carrier to obtain the copper foil; in addition, the reduction reaction at the cathode 12 can also supplement the oxidation reaction at the anode 11 with ferrous ions.
Further, as can be seen from the above reaction formulas (4) to (5), after the oxidation reaction of the anode 11, the ferrous ions in the second electrolyte solution are oxidized into ferric ions, and as the electrolysis reaction proceeds, the ferrous ions are continuously oxidized into ferric ions, thereby obtaining a third electrolyte solution. And the iron ions generated in the third electrolyte are introduced into the copper dissolving tank 2 again through the pipeline 3 to supplement the iron ions for the reaction of the formula (1) in the copper dissolving tank 2, and the metal copper in the copper dissolving tank is continuously dissolved along with the continuous reaction of the formula (1) to obtain copper ions. Therefore, the copper dissolving method provided by the application can realize continuous replenishment of copper ions by continuously circulating back and forth in the device, and finally the copper foil is obtained.
It will be appreciated that the first, second and third electrolytes described above in this application are continuously cycled between the electrolytic bath and the copper bath, and therefore the compositions of the three are identical.
It should be noted that, the pipeline connecting the copper dissolving tank and the electrolytic tank in the present application is not limited to the pipeline 3 and the pipeline 4 shown in fig. 1, and the arrangement of the pipeline may be selected according to actual requirements as long as the communication between the copper dissolving tank and the electrolytic tank can be realized, so that the electrolyte can circulate between the two. In addition, the manner of introducing the electrolyte in the electrolytic bath into the copper dissolving tank and returning the reaction solution in the copper dissolving tank to the electrolytic bath is not limited, and may be selected according to actual requirements, for example, the electrolyte in the electrolytic bath may be pumped into the copper dissolving tank, and after the copper dissolving reaction occurs in the copper dissolving tank, the reaction solution in the copper dissolving tank is pumped into the electrolytic bath, so as to realize the circulation of the electrolyte and the reaction solution between the copper dissolving tank and the electrolytic bath, and realize the gradual dissolution of the metal copper in the copper dissolving tank, thereby continuously providing copper ions for the electrolytic reaction.
In some embodiments, in step S10, the shape of the metallic copper is not limited, and may be, for example, a copper ball, a copper block, a copper sheet, etc., as long as the elemental copper can be provided for the copper dissolution reaction. In addition, the filling amount of the metal copper in the copper dissolving tank is not limited, and the metal copper can be filled according to actual requirements as long as continuous copper ions can be provided for the electrolytic reaction.
In some embodiments, the concentration of iron ions in the first electrolyte, the second electrolyte, and the third electrolyte are each independently 0.2g/L to 20g/L. For example, the concentration of ferric ion can be 0.5g/L,1g/L,3g/L,5g/L,7g/L,9g/L,11g/L,13g/L,15g/L,17g/L,19g/L or any range therebetween. Preferably, the concentration of iron ions in the electrolyte is 6g/L to 8g/L. The concentration of iron ions in the first electrolyte, the second electrolyte and the third electrolyte is controlled within a proper range, so that sufficient oxidant is provided for dissolving metal copper in the copper dissolving tank, and the continuous operation of electrolytic reaction in the electrolytic tank can be ensured.
In some embodiments, the first electrolyte solution, the second electrolyte solution, and the third electrolyte solution further each independently comprise ferrous ions and copper ions, wherein the ferrous ions are each independently at a concentration of 0.1g/L to 25g/L. For example, the ferrous ion concentration may be 0.5g/L,1g/L,3g/L,5g/L,7g/L,9g/L,11g/L,13g/L,15g/L,17g/L,19g/L,21g/L,23g/L or any combination thereof. Preferably, the concentration of the ferrous ions is 2 g/L-25 g/L. The concentration of the ferrous ions in the first electrolyte, the second electrolyte and the third electrolyte is controlled within a proper range, so that sufficient reactants are provided for an anodic reaction, and the sufficient concentration of the ferrous ions in the electrolytes is ensured, thereby ensuring the continuous oxidation-reduction reaction in an electrolytic bath and a copper dissolving bath.
In some embodiments, the concentration of copper ions is from 40g/L to 100g/L. For example, the concentration of copper ions can be 45g/L,50g/L,55g/L,60g/L,65g/L,70g/L,75g/L,80g/L,85g/L,90g/L,95g/L or any range therebetween. Preferably, the concentration of the copper ions is 45g/L to 95g/L. The concentration of copper ions is controlled within the above range, which can provide sufficient copper ions for the electrolytic reaction and is advantageous for promoting the electrolytic reaction.
In some embodiments, the first electrolyte, the second electrolyte, and the third electrolyte further each independently comprise one or more of sulfuric acid, chloride ions, and an acidic copper plating additive.
In some embodiments, the concentration of the sulfuric acid is each independently 80g/L to 250g/L. For example, the concentration of sulfuric acid may be 100g/L,130g/L,150g/L,180g/L,210g/L,230g/L or any combination thereof. Preferably, the concentration of the sulfuric acid is 100 g/L-200 g/L. The concentration control of the sulfuric acid provided in the application is in the range, so that the sulfate with enough concentration can be generated in the electrolyte, and meanwhile, the sulfate anions with single components in the electrolyte can also be used for ensuring the stability of the quality of an electroplated product.
In some embodiments, the concentration of the chloride ions is each independently from 5ppm to 100ppm. For example, the concentration of the chloride ion may be 10ppm,20ppm,30ppm,40ppm,50ppm,60ppm,70ppm,80ppm,90ppm or in the range of any of the above values. Preferably, the concentration of the chloride ion is 10ppm to 95ppm.
In the present embodiment, the concentration unit ppm (parts per million) of chloride ions is a concentration expressed by parts per million of solute in the total solution.
In some embodiments, the acidic copper-plating additive comprises one or more of a complexing agent, an accelerator, and an inhibitor; preferably, the complexing agent comprises at least one of potassium sodium tartrate, sodium citrate, disodium ethylene diamine tetraacetate and triethanolamine, the accelerator comprises at least one of sodium polydithio-dipropyl sulfonate and sodium 3-mercapto-1-propane sulfonate, and the inhibitor comprises polyethylene glycol.
The application provides a copper dissolving tank filled with metal copper in the copper dissolving method of the electrolytic copper foil, the copper dissolving tank filled with the metal copper is simple in structure, safe and easy to operate in production, and can supplement the metal copper into the copper dissolving tank at any time, so that the filling amount of the metal copper in the copper dissolving tank can be controlled, and the concentration of copper ions in the copper dissolving tank can be controlled. For the copper jar that dissolves of traditional copper foil, the copper efficiency is higher in the copper method that dissolves that this application provided, and used device is saved space more moreover also, and the device need not heating and ventilates, and the pipeline is simple moreover. In addition, the copper dissolving method provided by the application does not need to use copper oxide with higher price, and the cost can be greatly reduced. In addition, compared with a method using a phosphor copper ball as an anode, the copper dissolving method provided by the application can greatly save manpower, improve production efficiency and is beneficial to environmental protection. The method provided by the application has the advantages of simple process, less equipment, no requirement on environmental parameters such as temperature and pressure in the copper dissolving process, and convenience in implementation.
Examples
The following examples more particularly describe the disclosure of the present application for specific embodiments that are intended as illustrative only, since various modifications and changes within the scope of the disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the following examples are on a weight basis, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the equipment used in the examples is commercially available.
Example 1
A copper dissolving method of electrolytic copper foil comprises the following steps:
(1) Providing a copper dissolving tank filled with metal copper;
(2) Introducing a first electrolyte containing iron ions into a copper dissolving tank to dissolve the surface of metal copper to obtain a reaction solution containing copper ions and ferrous ions;
(3) Introducing the reaction solution into an electrolytic bath to supplement copper ions and ferrous ions into the electrolyte to obtain a second electrolyte;
(4) Carrying out electrolytic reaction on the second electrolyte so as to ensure that copper ions and ferrous ions are reduced into copper simple substances and oxidized into iron ions respectively to obtain a third electrolyte;
(5) And introducing a third electrolyte into the copper dissolving tank to continuously dissolve the surface of the metal copper.
The concentrations of iron ions in the first electrolyte, the second electrolyte and the third electrolyte are all 6g/L, the concentrations of ferrous ions are all 6g/L, the concentrations of Copper ions are all 40g/L, the concentrations of sulfuric acid are all 80g/L, the concentrations of chloride ions are all 5ppm, and the acidic Copper plating additives are Australian brand acidic Copper plating organic additives Copper A and Copper B.
Example 2
A copper dissolving method of electrolytic copper foil comprises the following steps:
(1) Providing a copper dissolving tank filled with metal copper;
(2) Introducing a first electrolyte containing iron ions into a copper dissolving tank to dissolve the surface of metal copper to obtain a reaction solution containing copper ions and ferrous ions;
(3) Introducing the reaction solution into an electrolytic bath to supplement copper ions and ferrous ions into the electrolyte to obtain a second electrolyte;
(4) Carrying out electrolytic reaction on the second electrolyte so as to ensure that copper ions and ferrous ions are reduced into copper simple substances and oxidized into iron ions respectively to obtain a third electrolyte;
(5) And introducing a third electrolyte into the copper dissolving tank to continuously dissolve the surface of the metal copper.
The concentrations of iron ions in the first electrolyte, the second electrolyte and the third electrolyte are all 20g/L, the concentrations of ferrous ions are all 25g/L, the concentrations of Copper ions are all 100g/L, the concentrations of sulfuric acid are all 250g/L, the concentrations of chlorine ions are all 100ppm, and the acidic Copper plating additives are Australian brand acidic Copper plating organic additives Copper A and Copper B.
Example 3
A copper dissolving method of electrolytic copper foil comprises the following steps:
(1) Providing a copper dissolving tank filled with metal copper;
(2) Introducing a first electrolyte containing iron ions into a copper dissolving tank to dissolve the surface of metal copper to obtain a reaction solution containing copper ions and ferrous ions;
(3) Introducing the reaction solution into an electrolytic bath to supplement copper ions and ferrous ions into the electrolyte to obtain a second electrolyte;
(4) Carrying out electrolytic reaction on the second electrolyte so as to respectively reduce copper ions and ferrous ions into copper simple substances and oxidize the copper simple substances and the ferrous ions into iron ions, thereby obtaining a third electrolyte;
(5) And introducing a third electrolyte into the copper dissolving tank to continuously dissolve the surface of the metal copper.
The concentrations of iron ions in the first electrolyte, the second electrolyte and the third electrolyte are all 8g/L, the concentrations of ferrous ions are all 15g/L, the concentrations of Copper ions are all 70g/L, the concentrations of sulfuric acid are all 165g/L, the concentrations of chloride ions are all 50ppm, and the acidic Copper plating additives are Australian brand acidic Copper plating organic additives Copper A and Copper B.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for dissolving copper in an electrolytic copper foil, comprising:
providing a copper dissolving tank filled with metal copper;
introducing a first electrolyte containing iron ions into the copper dissolving tank to dissolve at least part of the surface of the metal copper to obtain a reaction solution containing the copper ions and ferrous ions;
introducing the reaction solution into an electrolytic bath, and supplementing copper ions and ferrous ions into the first electrolyte to obtain a second electrolyte;
carrying out electrolytic reaction on the second electrolyte so as to ensure that the copper ions and the ferrous ions are respectively reduced into copper simple substances and oxidized into iron ions, thereby obtaining a third electrolyte; and
and introducing the third electrolyte into the copper dissolving tank to continuously dissolve at least part of the surface of the metal copper.
2. The method according to claim 1, wherein the concentrations of iron ions in the first electrolyte, the second electrolyte and the third electrolyte are each independently 0.2g/L to 20g/L.
3. The method according to claim 1, wherein the concentrations of iron ions in the first electrolyte, the second electrolyte and the third electrolyte are each independently 6g/L to 8g/L.
4. The method according to any one of claims 1 to 3, wherein the first electrolyte, the second electrolyte and the third electrolyte further each independently contain ferrous ions and copper ions, wherein the ferrous ions are each independently at a concentration of 0.1g/L to 25g/L.
5. The method according to claim 4, wherein the concentration of the ferrous ions is 2g/L to 25g/L.
6. The method according to claim 4, wherein the concentration of the copper ions is 40g/L to 100g/L.
7. A method according to any one of claim 1, wherein the first, second and third electrolytes each independently further comprise one or more of sulphuric acid, chloride ion and an acidic copper plating additive.
8. The method for dissolving copper according to claim 7, wherein the concentration of the sulfuric acid is 80g/L to 250g/L.
9. A method for dissolving copper according to claim 7, wherein the concentrations of said chloride ions are each independently 5ppm to 100ppm.
10. The method of dissolving copper in claim 7, wherein said acidic copper plating additive comprises one or more of a complexing agent, an accelerator, and an inhibitor;
optionally, the complexing agent comprises at least one of potassium sodium tartrate, sodium citrate, disodium edetate, and triethanolamine;
optionally, the accelerator comprises at least one of sodium polydithio dipropyl sulfonate and sodium 3-mercapto-1-propane sulfonate;
optionally, the inhibitor comprises polyethylene glycol.
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| CN202211173834.3A CN115386921A (en) | 2022-09-26 | 2022-09-26 | Copper dissolving method for electrolytic copper foil |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211173834.3A CN115386921A (en) | 2022-09-26 | 2022-09-26 | Copper dissolving method for electrolytic copper foil |
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Application publication date: 20221125 |