CN113430586B - Method for improving mechanical property of electrolytic copper foil and additive used by method - Google Patents
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000011889 copper foil Substances 0.000 title claims abstract description 104
- 239000000654 additive Substances 0.000 title claims abstract description 55
- 230000000996 additive effect Effects 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000013078 crystal Substances 0.000 claims abstract description 78
- 239000010949 copper Substances 0.000 claims abstract description 35
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- -1 polydithio-dipropyl Polymers 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005137 deposition process Methods 0.000 claims description 6
- 230000009647 facial growth Effects 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- 230000010287 polarization Effects 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 230000012010 growth Effects 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 12
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 18
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000005728 strengthening Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ZTYHBUKJQADEGW-UHFFFAOYSA-N C(=O)=C1C(C=CC=C1)NC1=CC=CC=C1 Chemical compound C(=O)=C1C(C=CC=C1)NC1=CC=CC=C1 ZTYHBUKJQADEGW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/12—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention relates to a method for improving the mechanical property of an electrolytic copper foil and an additive used by the method, belongs to the field of lithium ion batteries, and aims to solve the problems that the existing electrolytic copper foil is weaker in mechanical property, the tensile property of the existing electrolytic copper foil can be reduced along with the reduction of the thickness of the existing electrolytic copper foil, the process with the mechanical property of the existing electrolytic copper foil with strong pertinence generally has high cost, high process difficulty and the like. The method can effectively reduce the cost and the pollution; the modification treatment mode is simple and efficient, and the additional process is disordered; the growth orientation of copper crystal grains can be induced, and the orientation of a (220) crystal face is enhanced; meanwhile, the grain refinement can be realized, and the mechanical property of the copper foil is enhanced.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a method for improving the mechanical property of an electrolytic copper foil and an additive used by the method.
Background
The electrolytic copper foil is a metal foil, is an important raw material in the electronic and electrical industries, and is mainly used for manufacturing copper clad laminates, printed circuit boards, lithium batteries and the like. With the miniaturization of electronic devices, the continuous development of printed circuit surface mounting technology and the continuous increase of the requirements of multilayer printed circuit boards, the ultrathin high-performance electrolytic copper foil with few defects, fine grains, lower roughness, high strength, good ductility and wide application range is realized.
The quality of the electrolytic copper foil is mainly determined by the organization structure, the impurity content and the like of the electrolytic copper foil, and if the high-quality copper foil is obtained, the current density, the temperature of the electrolyte, the liquid inlet mode and the liquid inlet amount of an electrolytic bath, additives and the like must be strictly controlled. The additive is the most main control factor, and practice proves that adding a proper amount of additive is an effective measure for obtaining high-quality electrolytic copper foil with compact structure, smooth surface and low impurity content.
According to a fine-grain strengthening mechanism, the strength and toughness of the material can be improved after the internal crystal grains of the metal are refined, but the thickness of the copper foil only has a single-layer crystal grain, and the effect of improving the mechanical property of the copper foil is weakened by the fine-grain strengthening mechanism. The growth orientation of copper crystals is induced by using a proper additive, the orientation of (220) crystal faces is enhanced, the mechanical property of the copper foil can be effectively enhanced, and the difficulty of project research is the use of the proper additive. And at present, no scheme for modifying the additive for the electrolytic copper foil exists.
Disclosure of Invention
The invention provides a method for improving the mechanical property of an electrolytic copper foil and provides a used additive, aiming at solving the problems that the existing electrolytic copper foil is weaker in mechanical property, the tensile property of the existing electrolytic copper foil is reduced along with the reduction of the thickness of the existing electrolytic copper foil, and the process with the strong mechanical property of the electrolytic copper foil generally has high cost, high process difficulty and the like.
The invention aims to:
1. the performance of the electrolytic copper foil can be enhanced in a simple, efficient and low-cost manner;
2. the grain refinement of the copper foil can be realized;
3. the preferred orientation of copper crystal grains of the copper foil is realized, and the texture coefficient of the electrolytic copper foil in a specific direction is improved;
4. a large amount of dislocation and substructure are generated in the electrolytic copper foil in the electrolytic deposition process through the action of a proper additive, and the mechanical property of the electrolytic copper foil is improved.
In order to achieve the purpose, the invention adopts the following technical scheme.
A method for improving the mechanical property of electrolytic copper foil,
the method comprises the following steps:
in the preparation process of the electrolytic copper foil, the crystal face growth trend of crystal grain crystals in the copper foil is controlled, the (220) crystal face growth of the copper crystal grains is promoted, the texture coefficient of the copper crystal grains on the (220) crystal face is increased, and/or the cathode polarization in the copper deposition process is increased, and the copper crystal grains are refined.
According to the research of researchers, the texture coefficient of the electrolytic copper foil has great influence on the mechanical property of the electrolytic copper foil, so that the mechanical property of the electrolytic copper foil is improved in a mode of improving the texture coefficient of the electrolytic copper foil, the texture coefficient can directly influence the tensile strength and the ductility of the electrolytic copper foil, the cathode polarization in the deposition process is increased, the effect of refining crystal grains is further realized, and the refined crystal grains are known to be capable of comprehensively optimizing various mechanical properties of metal materials.
As a preference, the first and second liquid crystal compositions are,
the control of the crystal face growth trend of crystal grains in the copper foil is realized by adding an additive into an electrolyte used for electrolyzing the copper foil;
the additive contains ether bond and/or carbonyl and/or sulfonyl and/or amino and/or hydroxyl and/or sulfydryl;
the concentration of the additive is 0.005-0.015 mol/L.
Compared with other strengthening modes, the method disclosed by the invention has the characteristics of low cost, simplicity and high efficiency by adopting the mode of the additive to improve the mechanical property of the electrolytic copper foil, and in the existing technical scheme, researchers do not have relevant researches on improving the mechanical property of the electrolytic copper foil through the additive.
In the research process, the research personnel of the invention find that the crystals of the copper crystals mainly grow epitaxially at the beginning of the electrodeposition of the electrolytic copper foil, namely the surface of the titanium roller has great influence on the nucleation and growth of the initial copper crystals; in the later growth period, the influence of the electrodeposition conditions on the copper crystallization becomes more and more obvious along with the increase of the thickness of the copper foil, namely, the state of each crystal face on the copper crystallization has obvious influence on the subsequent deposition process. If proper additives are added in the electrolytic copper foil production process, preferential adsorption can be carried out on the specific crystal face of the crystal so as to inhibit texture generation. And at the beginning of deposition, metal atoms are adsorbed on the surface of the cathode. When the additive is present in the solution, the additive will significantly affect the deposition process of the metal ions, mainly the adsorption process of the metal. Many additives can be adsorbed on the surface of the cathode to form a compact adsorption layer, and the discharge process of metal ions or the surface diffusion of metal adsorption atoms is hindered, so that a coating with fine grains is obtained. The various effects of the additives on the coating are due to their diffusion depletion, adsorption polarization, and possible contamination of the coating with reduction products.
Therefore, the specific additive is selected, and the mechanical property of the electrolytic copper foil can be effectively optimized.
Further, the following four categories are classified according to the effects produced:
additives of type I: the crystal contains ether bonds and/or hydroxyl groups, and can be selectively adsorbed on a certain crystal face to realize the effect of inhibiting the growth of a certain orientation texture;
class II additives: the crystal contains carbonyl and/or sulfonyl, which can be selectively adsorbed on certain crystal faces, and the effect of promoting the growth of certain orientation texture is realized through the difference of adsorption energy;
group III additives: the copper-based composite material contains sulfydryl, can be uniformly adsorbed on each copper crystal face, can weaken the growth orientation of crystal grains, and assists in enhancing the grain refining effect;
additives of class IV: contains sulfonyl and/or amino and/or hydroxyl groups, and has stronger adsorbability to the titanium crystal face than the copper crystal face, enabling effective grain refinement to be actively achieved.
An additive used in a method for improving the mechanical property of an electrolytic copper foil,
the additive contains ether bond, hydroxyl, sulfydryl, amino, carbonyl and/or sulfonyl.
The various groups can be cooperated to generate a very excellent mechanical property improvement effect. For example, ether bonds have very obvious selectivity on three crystal planes of copper crystal grains, and the adsorption energy on the (111) plane of the copper crystal grains is much larger than that on the other two crystal planes, which shows that the ether bonds can well hinder the growth of the (111) crystal plane and play a role in inhibiting the (111) crystal plane texture. And for example, the carbonyl and the sulfonyl have obvious adsorbability on three crystal faces of copper grains, the carbonyl has weak adsorbability on the three crystal faces, the sulfonyl has strong adsorbability on the three crystal faces, and the sulfonyl has relatively strong adsorbability on a Cu (111) crystal face, so that the copper foil has certain capability of realizing oriented growth of the copper foil and changing the texture of the copper foil. The hydroxyl has obvious selectivity on three crystal faces of the copper crystal grains, the adsorptivity on the three crystal faces is similar, but the adsorptivity on the (220) crystal face is slightly stronger than that on the other two crystal faces, the texture coefficient of the copper foil (220) crystal face can be reduced theoretically, and the effect of crystal grain refinement can be realized actually.
The sulfydryl has almost the same adsorbability on the (111) crystal face, the (200) crystal face and the (220) crystal face of the copper crystal grain, can be adsorbed on the surface of each crystal face of the copper foil, increases the cathode polarization on the premise of keeping the texture coefficient, realizes a good crystal grain refining effect, and further realizes the effect of strengthening the mechanical property of the copper foil.
The amino and hydroxyl have relatively similar effects, but in fact sulfonyl, amino and hydroxyl also have extremely strong adsorbability on a titanium roller matrix, and the adsorbability on a Ti (101) crystal face is far greater than that on a copper crystal face, so that when the three are used, the three are preferentially adsorbed on the surface of the titanium roller actually, the growth of copper crystal grains is hindered in the transverse direction, the growth direction of the (220) crystal face texture perpendicular to the copper foil is changed, the internal stress of the copper foil is improved, and the effect of optimizing the mechanical property of the copper foil is realized.
An additive used in the method is sodium polydithio-dipropyl sulfonate.
An additive for use in the above method, said additive being polyethylene glycol.
An additive for use in the above process, said additive being a polyethyleneimine.
An additive used in the method is carbonyl diphenylamine.
The four additives are all additives with better practical effect after being optimized, the optimal concentration is basically 0.01-0.015 mol/L, and good modification effect can be realized by adopting extremely low concentration.
The invention has the beneficial effects that:
1) The method provides a distinctive copper foil mechanical property optimization mode, and can effectively reduce cost and pollution;
2) The modification treatment mode is simple and efficient, and the additional process is disordered;
3) The growth orientation of copper crystal grains can be induced, and the orientation of a (220) crystal face is enhanced;
4) Meanwhile, the grain refinement can be realized, and the mechanical property of the copper foil is enhanced.
Drawings
FIG. 1 is a graph showing the results of measurement of texture coefficients of the electrolytic copper foil obtained in example 1.
FIG. 2 is a graph showing the results of measurement of texture coefficients of the electrolytic copper foil prepared in comparative example 1.
FIG. 3 is an SEM representation of the matte side of the electrolytic copper foil obtained in example 1.
FIG. 4 is an SEM representation of the matte side of the electrolytic copper foil obtained in comparative example 1.
FIG. 5 is an SEM representation of the matte side of the electrolytic copper foil obtained in example 2.
FIG. 6 is an SEM representation of the matte side of the electrolytic copper foil obtained in example 3.
FIG. 7 is a graph showing the results of measurement of texture coefficients of the electrolytic copper foil obtained in example 4.
FIG. 8 is an SEM representation of the matte side of the electrolytic copper foil obtained in example 4.
Detailed Description
The invention is described in further detail below with reference to specific embodiments and the attached drawing figures. Those skilled in the art will be able to implement the invention based on these teachings. Furthermore, the embodiments of the present invention described in the following description are generally only a part of the embodiments of the present invention, and not all of the embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Unless otherwise specified, all the raw materials used in the examples of the present invention are commercially available or available to those skilled in the art; unless otherwise specified, the methods used in the examples of the present invention are all those known to those skilled in the art.
Unless otherwise stated, the basic formula adopted in the embodiment of the invention is copper sulfate/sulfuric acid aqueous solution, and the specific concentrations are as follows: 0.5 mol/L copper sulfate and 1.0 mol/L sulfuric acid.
Example 1
The additives selected in this example were: sodium polydithio-dipropyl sulfonate, and the addition amount of the additive is as follows: 0.01 mol/L.
The copper foil is prepared by the process of preparing the industrial conventional copper foil. The specific process comprises the following steps: controlling the current density to be 5A/m 2 。
The prepared electrolytic copper foil is detected according to the national standard GB/T-5230, and the detection shows that the tensile strength of the prepared electrolytic copper foil is 476.6 MPa. Further, the measurement results of the texture coefficients of the Cu (111), cu (200) and Cu (220) crystal planes were obtained as shown in FIG. 1. In the figure: a is a smooth surface (right column) of the electrolytic copper foil, and b is a matte surface (left column) of the electrolytic copper foil.
Comparative example 1
The procedure is as in example 1, except that: no additives were added.
The prepared electrolytic copper foil is detected according to the national standard GB/T-5230, and the detection shows that the tensile strength of the prepared electrolytic copper foil is 325.24 MPa. Further, the measurement results of the texture coefficients of the crystal planes of Cu (111), cu (200) and Cu (220) were measured, and are shown in FIG. 2. In the figure: a is a smooth surface (right column) of the electrolytic copper foil, and b is a rough surface (left column) of the electrolytic copper foil.
As is apparent from comparison between FIG. 1 and FIG. 2, the use of the additive can significantly improve the mechanical properties of the electrodeposited copper foil. And SEM characterization is performed on example 1 and comparative example 1, wherein an SEM characterization graph of the rough surface of the electrolytic copper foil prepared in example 1 is shown in FIG. 3, and an SEM characterization graph of the rough surface of the electrolytic copper foil prepared in comparative example 1 is shown in FIG. 4. As can be seen from the figure, the surface structure of the electrolytic copper foil is obviously changed after the additive is used, an obvious grain refinement effect is formed, an irregular convex structure is reduced, and the texture orientation of the copper foil is improved.
Example 2
The procedure is as in example 1, except that the additive is polyethylene glycol.
The prepared electrolytic copper foil is detected according to the national standard GB/T-5230, and the detection shows that the tensile strength of the prepared electrolytic copper foil is 451.45 MPa. The SEM representation of the matte surface of the obtained electrolytic copper foil is shown in FIG. 5.
As is apparent from fig. 5, the surface of the electrodeposited copper foil is very clearly grain-refined after the addition of the alcohol additive, and disordered protrusions are significantly reduced as in fig. 4.
Example 3
The procedure is as in example 1, except that the additives are 0.05 mol/L of diethyl ether and 0.05 mol/L of polyethyleneimine.
The prepared electrolytic copper foil is detected according to the national standard GB/T-5230, and the detection shows that the tensile strength of the prepared electrolytic copper foil is 511.61 MPa. The SEM characterization of the matte side of the obtained electrolytic copper foil is shown in FIG. 6.
It is obvious from fig. 6 that after the ether and amine additives are added, the growth direction of the copper foil crystal grains is obviously changed, and obvious refinement is generated, the texture characteristics of the copper foil are changed, and the mechanical property of the copper foil is obviously improved.
Example 4
The procedure is as in example 1, except that the additives are 0.005 mol/L sodium polydithio-dipropyl sulfonate, 0.005 mol/L polyethylene glycol and 0.005 mol/L polyethyleneimine.
The prepared electrolytic copper foil is detected according to the national standard GB/T-5230, and the detection shows that the tensile strength of the prepared electrolytic copper foil is 534.8 MPa. Further, the measurement results of the texture coefficients of the Cu (111), cu (200) and Cu (220) crystal planes were obtained, and are shown in FIG. 7. In the figure: a is a smooth surface (right column) of the electrolytic copper foil, and b is a rough surface (left column) of the electrolytic copper foil.
As is apparent from FIG. 7, the additive significantly improves the texture coefficient of the Cu (220) crystal plane of the rough surface of the electrolytic copper foil, so that the electrolytic copper foil produces a significant strengthening effect. Specifically, an SEM characteristic image of the electrodeposited copper foil produced in this example is shown in fig. 8. Under the coordination effect of each additive, the copper foil crystal grains are obviously refined, and the orientation growth trend is more obvious.
Claims (1)
1. A method for improving the mechanical property of an electrolytic copper foil is characterized by comprising the following steps:
in the preparation process of the electrolytic copper foil, the crystal face growth trend of crystal grain crystals in the copper foil is controlled, the (220) crystal face growth of the copper crystal grains is promoted, the texture coefficient of the copper crystal grains on the (220) crystal face is increased, and/or the cathode polarization in the copper deposition process is increased, and the copper crystal grains are refined;
the control of the crystal face growth trend of crystal grains in the copper foil is realized by adding an additive into an electrolyte used for electrolyzing the copper foil;
the electrolyte is a copper sulfate/sulfuric acid aqueous solution;
the concentration of the additive is 0.005-0.015 mol/L;
the additive is sodium polydithio-dipropyl sulfonate, or the additive is polyethylene glycol, or the additive is diethyl ether and polyethyleneimine, or the additive is sodium polydithio-dipropyl sulfonate, polyethylene glycol and polyethyleneimine.
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| CN1077913C (en) * | 1997-11-26 | 2002-01-16 | 孙乐之 | Engine fuel additive for eliminating smoke |
| JP5730742B2 (en) * | 2011-10-25 | 2015-06-10 | 古河電気工業株式会社 | Electrolytic copper foil for lithium ion secondary battery and method for producing the same |
| JP6067256B2 (en) * | 2012-06-27 | 2017-01-25 | 古河電気工業株式会社 | Electrolytic copper foil, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| CN111286765B (en) * | 2018-12-06 | 2021-11-19 | 湖北工程学院 | Electrolytic copper foil and preparation method and application thereof |
| CN111172567B (en) * | 2020-01-17 | 2021-07-16 | 广东嘉元科技股份有限公司 | Preparation method of extra-thin electrolytic copper foil for general-strength lithium ion battery |
| CN111304700A (en) * | 2020-03-26 | 2020-06-19 | 深圳市惟华电子科技有限公司 | Preparation method of reverse copper foil |
| CN111455416B (en) * | 2020-05-29 | 2021-02-09 | 佛冈建滔实业有限公司 | Preparation process of high-mechanical-property electrolytic copper foil of high-precision circuit board |
| CN112111761B (en) * | 2020-09-07 | 2021-09-21 | 浙江大学 | Electrolyte of high-elongation electrolytic copper foil and application thereof |
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Inventor after: Tang Yiping Inventor after: Jiang Chenhao Inventor after: Zhang Jianli Inventor after: Chen Qiang Inventor after: Hou Guangya Inventor before: Tang Yiping Inventor before: Jiang Chenhao Inventor before: Zhang Jianli Inventor before: Chen Qiang Inventor before: Hou Guangya |