WO2020034929A1 - Anti-oxidation electrochemical treatment method for copper material - Google Patents

Anti-oxidation electrochemical treatment method for copper material Download PDF

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WO2020034929A1
WO2020034929A1 PCT/CN2019/100291 CN2019100291W WO2020034929A1 WO 2020034929 A1 WO2020034929 A1 WO 2020034929A1 CN 2019100291 W CN2019100291 W CN 2019100291W WO 2020034929 A1 WO2020034929 A1 WO 2020034929A1
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formate
electrochemical
copper foil
copper
reconstruction
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PCT/CN2019/100291
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French (fr)
Chinese (zh)
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郑南峰
彭健
吴炳辉
毛和旭
郝树强
符昂
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厦门大学
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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
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/02—Electrolytic coating other than with metals with organic materials

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  • the invention belongs to the field of material surface treatment, and particularly relates to an oxidation-resistant electrochemical treatment method for a copper material.
  • Copper is one of the oldest base metal materials used by humans. Copper has very good electrical conductivity (second only to silver), thermal conductivity, excellent formability and lower price, and is widely used in the fields of electrical power industry, machinery and vehicle manufacturing industry, chemical industry, construction industry, defense industry, etc. . However, copper materials are easily oxidized in the natural environment, and the surface is easily corroded, thereby degrading their physical and chemical properties, which manifests as a rapid decline in electrical and thermal conductivity, which limits their applications.
  • the main anti-oxidation and anti-corrosion surface treatment methods of copper are:
  • a relatively inert metal such as gold, palladium, silver, or chromium, is plated on the surface of the copper material by chemical plating or vacuum evaporation.
  • organic stabilizers introduce a small amount of organic stabilizers, such as amines, aldehydes, phenols, and carboxylic acids, to reduce the oxide film on the surface of the copper material to metallic copper and inhibit its oxidation.
  • organic stabilizers such as amines, aldehydes, phenols, and carboxylic acids
  • CN105970261A discloses a chrome-free treatment process for preventing oxidation of copper foil. Specifically, the copper foil electroplated from the green foil is subjected to a pickling pretreatment, followed by a roughening process, Curing process, blackening process, galvanizing process, oxidation prevention process, organic film process and drying process. While improving the oxidation resistance of copper foil, the use of chrome metal and other harmful elements to the human body and the environment is avoided. However, zinc sulphate and other environmentally hazardous metals are introduced during the operation, and higher temperatures are required for drying. At the same time, the operation steps are complicated, and a long cycle will inevitably bring a lot of costs.
  • EP0541997A2 discloses a surface treatment method of copper foil for printed circuits.
  • the surface of the copper foil is plated with a passivation film of chromium oxide or zinc oxide, which can resist 270 ° C. high temperature.
  • chromium oxide or zinc oxide which can resist 270 ° C. high temperature.
  • CN106399996A discloses a copper foil anti-oxidation treatment liquid, a preparation method and a device thereof.
  • the copper foil anti-oxidation treatment liquid contains oil hydroxybenzotriazole, 0.05-0.1 g / L, 2-mercaptobenzotriazole 0.02 ⁇ 0.05g / L, silver nitrate 0.1 ⁇ 0.5g / L, sodium molybdate 0.1 ⁇ 0.5g / L, phosphoric acid 0.05 ⁇ 0.1g / L, boric acid 0.5 ⁇ 3g / L, the rest For pure water.
  • the obtained anti-oxidation passivation film is stable under high temperature conditions and does not contain zinc metal, which solves the problems of instability such as reduction in resistance of copper foil.
  • this method improves the oxidation resistance of copper powder, it is necessary to add expensive reagents such as benzotriazole and silver nitrate, which will inevitably bring cost increase.
  • the purpose of the present invention is to overcome the above drawbacks of anti-oxidation treatment of copper materials by using existing methods, and to provide a new anti-oxidation electrochemical treatment method of copper materials.
  • the present invention provides a method for electrochemically treating a copper material against oxidation.
  • the method includes using the copper material as a working electrode, and sequentially performing electrochemical reconstruction and electrochemical deposition in an electrolyte containing a stabilizer.
  • the stabilizer is a compound capable of providing formate, so that formate is adsorbed on the surface of the copper material.
  • the electrochemical treatment usually uses a three-electrode system, wherein the working electrode is a copper material, the reference electrode is preferably a saturated calomel electrode, and the counter electrode is preferably at least one of a platinum electrode, a graphite electrode, and a glassy carbon electrode.
  • the electrolyte is a mixed solution of a stabilizer and a polar solvent.
  • the weight ratio of the stabilizer to the polar solvent is from 1:10 to 1: 100, and more preferably from 1:15 to 1:90.
  • the stabilizer can be various existing compounds capable of providing formate, preferably formic acid and / or formate.
  • the specific examples of the formate include, but are not limited to, lithium formate, sodium formate, cesium formate, magnesium formate, aluminum triformate, potassium formate, ammonium formate, calcium formate, zinc formate, iron formate, copper formate, and strontium formate. At least one of barium formate, beryllium formate, nickel formate, cobalt formate, and manganese formate.
  • the mass ratio of the stabilizer to the copper material is preferably 10: 1 to 1: 10000.
  • the type of the polar solvent is not particularly limited in the present invention, and may be water and / or various polar organic solvents, and is preferably selected from water, amide solvents, alcohol solvents, ester solvents, and ethers. At least one of solvents.
  • the specific examples of the amide-based solvent include, but are not limited to, at least one of formamide, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, and dimethylpropionamide.
  • Specific examples of the alcohol-based solvent include, but are not limited to, at least one of a monohydric alcohol, a dihydric alcohol, and a polyhydric alcohol.
  • ester-based solvent examples include, but are not limited to, ethyl acetate, methyl acetate, n-butyl acetate, n-pentyl acetate, ethyl valerate, ethyl propionate, ethyl butyrate, ethyl lactate, At least one of ethyl nonanoate, triethyl phosphate, ethyl hexanoate, ethyl formate, ethyl cyclohexanoate, ethyl heptanoate and ethyl cinnamate.
  • ether-based solvent include, but are not limited to, at least one of methyl ether, diethyl ether, diphenyl ether, ethylene oxide, and tetrahydrofuran.
  • the pH of the electrolyte ranges from 4 to 13, and more preferably from 5 to 11.
  • the method for adjusting the pH of the electrolyte to the above range may generally include adding an acid or an alkali to the electrolyte. The specific operation is well known to those skilled in the art, and details are not described herein.
  • the purpose of the electrochemical reconstruction is to restructure the crystal plane of the copper material, so that it is at least partially converted from the original (111) or (100) crystal plane to the (110) crystal plane, so as to facilitate subsequent electrochemical deposition.
  • the electrochemical reconstruction may use at least one of cyclic voltammetry, square wave voltammetry, and differential pulse voltammetry.
  • the electrochemical window of the electrochemical reconstruction is preferably -5V to 5V, more preferably -2V to 1V, and most preferably -1V to 0.5V; the scanning speed is preferably 10 -1 to 10 3 mV / s, and more preferably It is 1 to 10 2 mV / s, and most preferably 5 to 20 mV / s.
  • the temperature of the electrochemical reconstruction is preferably -70 to 200 ° C, more preferably 10 to 100 ° C, and most preferably room temperature to 60 ° C.
  • the number of scanning cycles is preferably 1 to 1000 cycles, more preferably 1 to 100 cycles, and most preferably 1 to 10 cycles.
  • the purpose of the electrochemical deposition is to make the formate in the electrolyte adhere to the surface of the copper material by electroplating.
  • the electrochemical deposition may use at least one of a constant potential deposition method, a constant current deposition method, and an underpotential deposition method.
  • the potential range of the potentiostatic deposition method is preferably -5V to 5V, more preferably -5V to 0V, and most preferably -2V to 0V
  • the current range of the constant current deposition method is preferably 10 -3 to 10 3 mA / cm 2 , more preferably 10 -2 to 10 2 mA / cm 2 , and most preferably 10 -1 to 10 1 mA / cm 2 .
  • the temperature of the electrochemical deposition is preferably -70 to 200 ° C, more preferably 0 to 200 ° C, and most preferably room temperature to 60 ° C.
  • the time is preferably 0.1 to 1000min, more preferably 1 to 100min, and most preferably It is 5 to 30 minutes.
  • the electrochemical reconstruction and electrochemical deposition may adopt a sealed type or an open type, preferably a sealed type, so as to reduce external interference.
  • the present invention does not specifically limit the type of the copper-containing material, and it can be any existing copper material, including pure copper materials (copper copper, brass), copper alloys, etc., which can be specifically selected from copper foil, At least one of foamed copper, copper powder, copper cable, copper faucet, copper nanowire, and copper wire.
  • the present invention adopts an electrochemical method to allow formate to be plated on the surface of a copper material, and to achieve the adsorption of formate through the synergistic effect of electrochemical reconstruction and electrochemical deposition, thereby enhancing the oxidation resistance of the copper material.
  • the electrochemically treated copper material of the present invention has stronger oxidation resistance (including high temperature oxidation resistance), salt and alkali corrosion resistance and higher electrical conductivity than before treatment, and can be used for electric wires, printed circuit boards, and motors. , Transformers, sanitary and other fields.
  • the invention has simple operation, mild conditions, and low cost, and can achieve effective oxidation and corrosion treatment of various copper materials at normal temperature.
  • the copper material processed by the method provided by the present invention has good oxidation resistance, avoids the use of potentially toxic metals such as lead, chromium, cadmium or cyanide, and complies with the relevant provisions of the Environmental Protection Law of the People's Republic of China.
  • FIG. 1 is an SEM image of the unmodified copper foil in Example 1 placed in a 0.1M NaOH solution at room temperature for 10 hours, indicating that the unmodified copper foil is easily oxidized and corroded, and the surface becomes rough.
  • FIG. 2 is an SEM image of the formate-modified copper foil in Example 1 placed at room temperature in a 0.1M NaOH solution for 10 hours at room temperature, which shows that the surface of the copper foil after the formate modification is still smooth and flat, and the oxidation resistance is significantly enhanced.
  • FIG. 3 is an optical photograph of the unmodified plated copper in Example 7 which is left at room temperature for 24 h in a 3 wt% NaCl solution, which illustrates that the unmodified plated copper is easily oxidized and corroded, and the surface is dull.
  • FIG. 4 is an optical photo of the formate-modified copper plated in Example 7 placed at room temperature for 10 hours in a 3% by weight NaCl solution, illustrating that the surface of the copper foil after the formate modification is still smooth, uniform in color, and the oxidation resistance is significantly enhanced.
  • FIG. 5 is an x-ray diffraction spectrum of the copper before and after electrochemical reconstruction of the coated copper in Example 8.
  • the peak of the (110) crystal plane of the copper after the electrochemical reconstruction is significantly enhanced, indicating that formate has induced copper surface occurrence. Refactored.
  • Figure 1 is an SEM image of unmodified copper foil placed in a 0.1M NaOH solution at room temperature for 10 hours, indicating that the unmodified copper foil is easily oxidized and corroded, so that the surface becomes rough;
  • Figure 2 is formate modified copper foil at 0.1
  • the SEM image of M in NaOH solution at room temperature for 10 hours shows that the surface of the copper foil is smooth and flat, and the oxidation resistance is significantly enhanced after formate modification.
  • Cyclic voltammetry (scanning speed: 50mV / s, scanning range: -1.5 ⁇ 0.5V) was used to scan the surface of copper foil twice at 45 ° C.
  • the surface of the copper foil was electrochemically reconstructed.
  • the copper foil before and after the electrochemical reconstruction was subjected to an x-ray diffraction test.
  • the results showed that the (110) crystal plane of the copper foil after the electrochemical reconstruction had obvious x-ray diffraction peaks.
  • the enhancement indicates that formate induces remodeling of the copper surface.
  • the cyclic voltammetry technology (scanning speed: 50mV / s, scanning range: -1.5 to 0.5V) was used to scan the copper foil surface twice at 30 ° C to perform electrochemical reconstruction of the copper foil surface and the electrochemical weight was changed.
  • X-ray diffraction tests were performed on the copper foil before and after the formation, and the results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that formate induced copper surface reconstruction.
  • the current step technology was used for electrochemical deposition at a constant potential of -0.65V for 8 minutes, washed with ethanol, and blown with nitrogen to obtain an anti-oxidation copper foil.
  • the copper foil before and after the treatment was 0.1M.
  • the SEM test was performed after leaving the solution in NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
  • the copper foil before and after the treatment was placed in a 0.1M NaOH solution at room temperature for 10 hours and then subjected to SEM tests. The results showed that the formate-modified copper foil had a smoother and smoother surface, and its oxidation resistance was improved.
  • the x-ray diffraction test of the copper foil showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil was significantly enhanced after electrochemical reconstruction, indicating that formate induced the reconstruction of the copper surface.
  • a current step technology was used for electrochemical deposition at a constant potential of -0.68V for 15 minutes, and the mixture was washed with a mixed solvent of ethanol / H 2 O and dried with nitrogen to obtain an anti-oxidation copper foil.
  • the copper foil before and after the treatment was placed in a 0.1M NaOH solution at room temperature for 10 hours and then subjected to SEM tests. The results showed that the formate-modified copper foil had a smoother and smoother surface, and its oxidation resistance was improved.
  • Figure 3 is an optical photo of unmodified copper plated at room temperature in a 0.1M NaCl solution for 24 hours, illustrating that the unmodified copper plated is susceptible to oxidative corrosion and thus surface oxidation;
  • Figure 4 is a formate modified copper plated at 0.1M NaCl solution at room temperature The optical photo that was left for 10 hours showed that the surface of the copper foil was smooth and flat, and the oxidation resistance was significantly enhanced after formate modification.
  • the x-ray diffraction spectra before and after the electrochemical reconstruction of the coated copper are shown in FIG. 5. It can be seen from the results in FIG. 5 that the x-ray diffraction peak of the (110) crystal plane of the plated copper after electrochemical reconstruction is significantly enhanced, indicating that formate-induced copper surface reconstruction has occurred. Subsequent electrochemical deposition at 40 ° C with a constant potential of -0.6V for 10 min can obtain anti-oxidation coated copper. The copper before and after the treatment was placed in a 0.1M NaOH solution at room temperature for 10 hours and then subjected to SEM tests. Results It shows that the formate-modified copper has a smoother and smoother surface, and it can be seen that its oxidation resistance is improved.
  • Step 1 Surface cleaning. A copper foil with a length of 3 cm, a width of 1 cm, and a thickness of 25 m was placed in an ethanol solution of 1 wt% formic acid, washed with ultrasound for 5 minutes to remove surface organics and oxides, and dried by nitrogen purging.
  • Step two electrochemical reconstruction and electrochemical deposition.
  • Electrolyte solution prepare a 1 wt% sodium formate aqueous solution, and adjust the pH of the solution to 9;
  • Step 3 Wash with ethanol and dry.
  • the SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
  • Step 1 Surface cleaning. A copper foil with a length of 4 cm, a width of 2 cm, and a thickness of 30 ⁇ m was placed in an ethanol solution of 1.5% formic acid, and the surface organic matter and oxides were removed by ultrasonic washing for 3 min, and then dried by nitrogen purging.
  • Step two electrochemical reconstruction and electrochemical deposition.
  • Electrolyte solution prepare a 2 wt% sodium formate aqueous solution and adjust the pH of the solution to 10;
  • Step 3 Wash with ethanol and dry.
  • the SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
  • Step 1 Surface cleaning. A copper foil with a length of 3 cm, a width of 0.5 cm, and a thickness of 20 ⁇ m was placed in a 0.5 wt% formic acid in ethanol solution, ultrasonically washed for 8 minutes to remove surface organics and oxides, and dried by nitrogen purging.
  • Step two electrochemical reconstruction and electrochemical deposition.
  • Electrolyte solution prepare a 5 wt% sodium formate aqueous solution and adjust the pH of the solution to 8;
  • Step 3 Wash with ethanol and dry.
  • the SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
  • Step 1 Surface cleaning. A 5 cm long, 3 cm wide and 40 ⁇ m thick copper foil was taken and placed in a 2 wt% formic acid in ethanol solution, and the surface organic matter and oxides were removed by ultrasonic cleaning for 1 min, and then dried by nitrogen purging.
  • Step two electrochemical reconstruction and electrochemical deposition.
  • Electrolyte solution prepare a 10 wt% sodium formate aqueous solution, and adjust the pH of the solution to 10;
  • Step 3 Wash with ethanol and dry.
  • the SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
  • Step 1 Surface cleaning: take 25 ⁇ m thick copper foil, cut into 1cm ⁇ 3cm rectangular size, soak it in ethanol solution containing 1wt% formic acid, and sonicate for 5min, wash away the remaining organics and oxides on the surface, and then sonicate with ethanol Rinse 3 times and dry with a nitrogen purge.
  • Step 2 electrolyte preparation: the dried copper foil is used as the working electrode, the saturated calomel electrode is used as the reference electrode, and the platinum sheet electrode is used as the counter electrode.
  • Step 3 Electrochemical reconstruction and electrochemical deposition: At room temperature, using cyclic voltammetry (scanning speed: 10mV / s, scanning range: -1 to 0.5V), perform a scanning cycle at 45 ° C. Reconstruction.
  • the copper foil before and after electrochemical reconstruction was subjected to x-ray diffraction test. The results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that the formate induced
  • the copper surface was reconstituted; afterwards, it was deposited at a constant potential of -0.4V for 30 min to obtain an anti-oxidation copper foil.
  • Step 4 Wash with ethanol and dry.
  • the SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
  • Step 1 Surface cleaning: take 25 ⁇ m thick copper foil, cut into 1cm ⁇ 3cm rectangular size, soak it in ethanol solution containing 1wt% formic acid, and sonicate for 5min, wash away the remaining organics and oxides on the surface, and then sonicate with ethanol Rinse 3 times and dry with a nitrogen purge.
  • Step 2 electrolyte preparation: the dried copper foil is used as the working electrode, the saturated calomel electrode is used as the reference electrode, and the platinum sheet electrode is used as the counter electrode.
  • Step 3 Electrochemical reconstruction and electrochemical deposition: At room temperature, using cyclic voltammetry (scanning speed: 10mV / s, scanning range: -1 to 0.5V), perform a scanning cycle at 55 ° C. Reconstruction.
  • the copper foil before and after electrochemical reconstruction was subjected to x-ray diffraction test. The results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that the formate induced
  • the copper surface was restructured; afterwards, it was deposited at a constant potential of -1.0V for 30 minutes to obtain an anti-oxidation copper foil.
  • Step 4 Wash with ethanol and dry.
  • the SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
  • Step 1 Surface cleaning: take 25 ⁇ m thick copper foil, cut into 1 ⁇ 3cm 2 rectangles, soak it in an ethanol solution containing 1wt% formic acid, and sonicate for 5min, wash away the remaining organic matter and oxides on the surface, and then use ethanol Sonicate 3 times and dry with a nitrogen purge.
  • Step 2 electrolyte preparation: the dried copper foil is used as the working electrode, the saturated calomel electrode is used as the reference electrode, and the platinum sheet electrode is used as the counter electrode.
  • Step 3 Electrochemical reconstruction and electrochemical deposition: At room temperature, using cyclic voltammetry (scanning speed: 10mV / s, scanning range: -1 to 0.5V), scan for 3 cycles at 25 ° C. Reconstruction.
  • the copper foil before and after electrochemical reconstruction was subjected to x-ray diffraction test. The results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that the formate induced
  • the copper surface was reconstituted; afterwards, it was deposited at a constant potential of -0.7V for 30 min to obtain an oxidation-resistant copper foil.
  • Step 4 Wash with ethanol and dry.
  • the SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
  • Embodiment 16 is a diagrammatic representation of Embodiment 16:
  • Step 1 Surface cleaning: take 25 ⁇ m thick copper foil, cut into 1 ⁇ 3cm 2 rectangles, soak it in an ethanol solution containing 1wt% formic acid, and sonicate for 5min, wash away the remaining organic matter and oxides on the surface, and then use ethanol Sonicate 3 times and dry with a nitrogen purge.
  • Step 2 electrolyte preparation: the dried copper foil is used as the working electrode, the saturated calomel electrode is used as the reference electrode, and the platinum sheet electrode is used as the counter electrode.
  • Step 3 Electrochemical reconstruction and electrochemical deposition: at room temperature, using square wave voltammetry (scanning speed: 10mV / s, scanning range: -1 ⁇ 0.5V), scanning at 35 ° C for 5 cycles
  • the copper foil before and after electrochemical reconstruction was subjected to x-ray diffraction test.
  • the results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that formate Reconstruction of the copper surface was induced; then, a copper foil with anti-oxidation treatment was obtained by electrochemical deposition at a constant potential of -0.6V for 30 min.
  • Step 4 Wash with ethanol and dry.
  • the SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
  • Example 2 Surface treatment was performed on the copper foil according to the method of Example 1. The difference was that the step of electrochemical reconstruction using cyclic voltammetry was not included. Instead, the cleaned copper foil was subjected to potentiostatic electrochemistry in an electrolyte solution. After deposition, an anti-oxidation-treated copper foil was obtained, and the SEM test was performed. The results showed that the copper foil was left in a 0.1M NaOH solution at room temperature for 10 hours, and the entire surface was smooth and flat, but local oxidation corrosion appeared. Its oxidation resistance has been mentioned to a certain extent, but it still needs to be improved.

Abstract

The invention belongs to the field of material surface treatment, and specifically discloses an anti-oxidation electrochemical treatment method for a copper material. The method comprises using a copper material as a working electrode, and sequentially performing electrochemical reconstruction and electrochemical deposition in an electrolyte containing a stabilizer. The stabilizer is a compound capable of providing formate, such that formate is adsorbed on a surface of the copper material. The electrochemical method is used to enable plating of formate on the surface of the copper material, thereby enhancing the anti-oxidation ability of the copper material. The method is simple to operate; and has good conditions, low costs, and great industrial application prospects.

Description

一种铜材料抗氧化的电化学处理方法Anti-oxidation electrochemical treatment method of copper material 技术领域Technical field
本发明属于材料表面处理领域，具体涉及一种铜材料抗氧化的电化学处理方法。The invention belongs to the field of material surface treatment, and particularly relates to an oxidation-resistant electrochemical treatment method for a copper material.
背景技术Background technique
铜是人类使用历史最悠久的贱金属材料之一。铜具有非常好的导电性(仅次于银)、导热性及优良的成形性和较低的价格，广泛用于电气电力工业、机械和车辆制造工业、化学工业、建筑工业、国防工业等领域。但是，铜材料在自然环境中容易被氧化，表面容易被腐蚀，从而使其物理化学性能退化，表现为导电导热性的急速下降，限制了其应用。Copper is one of the oldest base metal materials used by humans. Copper has very good electrical conductivity (second only to silver), thermal conductivity, excellent formability and lower price, and is widely used in the fields of electrical power industry, machinery and vehicle manufacturing industry, chemical industry, construction industry, defense industry, etc. . However, copper materials are easily oxidized in the natural environment, and the surface is easily corroded, thereby degrading their physical and chemical properties, which manifests as a rapid decline in electrical and thermal conductivity, which limits their applications.
目前，铜的抗氧化防腐蚀表面处理方法主要有：At present, the main anti-oxidation and anti-corrosion surface treatment methods of copper are:
(1)表面镀金属：采用化学镀或者真空蒸镀的方法在铜材料表面镀一层相对惰性的金属，比如金、钯、银或铬。(1) Metal plating on the surface: a relatively inert metal, such as gold, palladium, silver, or chromium, is plated on the surface of the copper material by chemical plating or vacuum evaporation.
(2)采用偶联剂处理：采用钛酸酯或者硅烷偶联剂对铜材料表面进行包覆处理。(2) Coupling treatment: the surface of the copper material is coated with a titanate or a silane coupling agent.
(3)表面疏水化处理：油酸、油胺或硬脂酸盐构建疏水表面。(3) Surface hydrophobizing treatment: oleic acid, oleylamine or stearate constructs a hydrophobic surface.
(4)加入适量有机稳定剂：引入少量有机稳定剂，如胺、醛、酚和羧酸等，将铜材料表面的氧化膜还原为金属铜，并抑制其氧化。(4) Add an appropriate amount of organic stabilizers: introduce a small amount of organic stabilizers, such as amines, aldehydes, phenols, and carboxylic acids, to reduce the oxide film on the surface of the copper material to metallic copper and inhibit its oxidation.
在方法(1)中抗氧化效果较好，但是成本较高，而且工艺较为复杂。方法(2)～(4)中得到的铜材料能起到一定的抗氧化作用，但是处于腐蚀性环境下时，铜仍会慢慢氧化。In method (1), the antioxidant effect is better, but the cost is higher and the process is more complicated. The copper material obtained in methods (2) to (4) can play a certain role in anti-oxidation, but when it is in a corrosive environment, copper will still slowly oxidize.
对应方法(1)～(3)，CN105970261A公开了一种防止铜箔氧化的无铬化处理工艺，具体地，将生箔电镀成的铜箔经过酸洗预处理后，依次经过粗化工序、固化工序、黑化工序、镀锌工序、防氧化工序、有机膜工序和烘干工序。在提高铜箔抗氧化性的同时，避免了使用铬金属等对人体和环境有害的元素。但操作过程中引入了硫酸锌等对环境危害的金属，烘干需要较高的温度，同时操作步骤繁琐，周期较长必然会带来大量的成本。对应方法(1)，EP0541997A2公开了一种用于打印电路的铜箔的表面处理方法，在铜箔表面采用电镀的方法镀上一层氧化铬或者氧化锌的钝化膜，能够耐270℃的高温。但是由于处理过程中引入了铬，必然会对环境有一定的毒害作用。Corresponding to methods (1) to (3), CN105970261A discloses a chrome-free treatment process for preventing oxidation of copper foil. Specifically, the copper foil electroplated from the green foil is subjected to a pickling pretreatment, followed by a roughening process, Curing process, blackening process, galvanizing process, oxidation prevention process, organic film process and drying process. While improving the oxidation resistance of copper foil, the use of chrome metal and other harmful elements to the human body and the environment is avoided. However, zinc sulphate and other environmentally hazardous metals are introduced during the operation, and higher temperatures are required for drying. At the same time, the operation steps are complicated, and a long cycle will inevitably bring a lot of costs. Corresponding method (1), EP0541997A2 discloses a surface treatment method of copper foil for printed circuits. The surface of the copper foil is plated with a passivation film of chromium oxide or zinc oxide, which can resist 270 ° C. high temperature. However, due to the introduction of chromium in the process, it will certainly have a certain toxic effect on the environment.
对应方法(1)和(4)，CN106399996A公开了一种铜箔防氧化处理液及制备方法和设备，所述铜箔防氧化处理液含有油羟基苯并三氮唑0.05～0.1g/L、2-巯基苯并三氮唑0.02～0.05g/L、 硝酸银0.1～0.5g/L、钼酸钠0.1～0.5g/L、磷酸0.05～0.1g/L、硼酸0.5～3g/L，其余为纯水。所得的防氧化钝化膜在高温条件下稳定且不含锌金属，解决了铜箔的电阻降低等不稳定问题。然而，尽管这种方法提高了铜粉的抗氧化能力，但是需要加入苯并三氮唑和硝酸银等价格昂贵的试剂，由此必然会带来成本的提高。Corresponding to methods (1) and (4), CN106399996A discloses a copper foil anti-oxidation treatment liquid, a preparation method and a device thereof. The copper foil anti-oxidation treatment liquid contains oil hydroxybenzotriazole, 0.05-0.1 g / L, 2-mercaptobenzotriazole 0.02 ～ 0.05g / L, silver nitrate 0.1 ～ 0.5g / L, sodium molybdate 0.1 ～ 0.5g / L, phosphoric acid 0.05 ～ 0.1g / L, boric acid 0.5 ～ 3g / L, the rest For pure water. The obtained anti-oxidation passivation film is stable under high temperature conditions and does not contain zinc metal, which solves the problems of instability such as reduction in resistance of copper foil. However, although this method improves the oxidation resistance of copper powder, it is necessary to add expensive reagents such as benzotriazole and silver nitrate, which will inevitably bring cost increase.
上述抗氧化方法要么是处理价格昂贵，会污染环境，要么是处理温度较高，处理时间较长，因此，针对铜材料开发一种简单且高效的抗氧化耐腐蚀的表面处理方法是目前解决铜在电气电力工业、机械和车辆制造工业、化学工业、建筑工业、国防工业等领域应用的技术难题的主要途径。The above-mentioned anti-oxidation methods are either expensive to treat, will pollute the environment, or have high processing temperatures and long processing times. Therefore, the development of a simple and efficient oxidation and corrosion resistant surface treatment method for copper materials is currently addressing copper. The main ways to apply technical problems in the fields of electrical power industry, machinery and vehicle manufacturing industry, chemical industry, construction industry, national defense industry and so on.
发明内容Summary of the Invention
本发明的目的是为了克服采用现有方法对铜材料进行抗氧化处理的以上缺陷，而提供一种新的铜材料抗氧化的电化学处理方法。The purpose of the present invention is to overcome the above drawbacks of anti-oxidation treatment of copper materials by using existing methods, and to provide a new anti-oxidation electrochemical treatment method of copper materials.
具体地，本发明提供了一种铜材料抗氧化的电化学处理方法，其中，该方法包括将铜材料作为工作电极，在含有稳定剂的电解质中依次进行电化学重构和电化学沉积，所述稳定剂为能够提供甲酸根的化合物，以使得所述铜材料的表面吸附有甲酸根。该电化学处理通常采用三电极体系，其中，工作电极为铜材料，参比电极优选为饱和甘汞电极，对电极优选为铂电极、石墨电极和玻碳电极中的至少一种。Specifically, the present invention provides a method for electrochemically treating a copper material against oxidation. The method includes using the copper material as a working electrode, and sequentially performing electrochemical reconstruction and electrochemical deposition in an electrolyte containing a stabilizer. The stabilizer is a compound capable of providing formate, so that formate is adsorbed on the surface of the copper material. The electrochemical treatment usually uses a three-electrode system, wherein the working electrode is a copper material, the reference electrode is preferably a saturated calomel electrode, and the counter electrode is preferably at least one of a platinum electrode, a graphite electrode, and a glassy carbon electrode.
优选地，所述电解质为稳定剂和极性溶剂的混合溶液。Preferably, the electrolyte is a mixed solution of a stabilizer and a polar solvent.
优选地，所述稳定剂与极性溶剂的重量比为1︰10～1︰100，更优选为1︰15～1︰90。Preferably, the weight ratio of the stabilizer to the polar solvent is from 1:10 to 1: 100, and more preferably from 1:15 to 1:90.
所述稳定剂可以为现有的各种能够提供甲酸根的化合物，优选为甲酸和/或甲酸盐。其中，所述甲酸盐的具体实例包括但不限于：甲酸锂、甲酸钠、甲酸铯、甲酸镁、三甲酸铝、甲酸钾、甲酸铵、甲酸钙、甲酸锌、甲酸铁、甲酸铜、甲酸锶、甲酸钡、甲酸铍、甲酸镍、甲酸钴和甲酸锰中的至少一种。此外，所述稳定剂与所述铜材料的质量比优选为10︰1～1︰10000。The stabilizer can be various existing compounds capable of providing formate, preferably formic acid and / or formate. The specific examples of the formate include, but are not limited to, lithium formate, sodium formate, cesium formate, magnesium formate, aluminum triformate, potassium formate, ammonium formate, calcium formate, zinc formate, iron formate, copper formate, and strontium formate. At least one of barium formate, beryllium formate, nickel formate, cobalt formate, and manganese formate. In addition, the mass ratio of the stabilizer to the copper material is preferably 10: 1 to 1: 10000.
本发明对所述极性溶剂的种类没有特别的限定，可以为水和/或现有的各种极性有机溶剂，优选选自水、酰胺类溶剂、醇类溶剂、酯类溶剂和醚类溶剂中的至少一种。其中，所述酰胺类溶剂的具体实例包括但不限于：甲酰胺、二甲基甲酰胺、二乙基甲酰胺、二甲基乙酰胺、二乙基乙酰胺和二甲基丙酰胺中的至少一种。所述醇类溶剂的具体实例包括但不限于：一元醇、二元醇和多元醇中的至少一种。所述酯类溶剂的具体实例包括但不限于：乙酸乙酯、乙酸甲酯、乙酸正丁脂、乙酸正戊酯、戊酸乙酯、丙酸乙酯、丁酸乙酯、乳酸乙酯、壬酸乙酯、磷酸三乙酯、己酸乙酯、甲酸乙酯、环己甲酸乙酯、庚酸乙酯和肉桂酸乙酯中的至少一 种。所述醚类溶剂的具体实例包括但不限于：甲醚、***、二苯醚、环氧乙烷和四氢呋喃中的至少一种。The type of the polar solvent is not particularly limited in the present invention, and may be water and / or various polar organic solvents, and is preferably selected from water, amide solvents, alcohol solvents, ester solvents, and ethers. At least one of solvents. The specific examples of the amide-based solvent include, but are not limited to, at least one of formamide, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, and dimethylpropionamide. One. Specific examples of the alcohol-based solvent include, but are not limited to, at least one of a monohydric alcohol, a dihydric alcohol, and a polyhydric alcohol. Specific examples of the ester-based solvent include, but are not limited to, ethyl acetate, methyl acetate, n-butyl acetate, n-pentyl acetate, ethyl valerate, ethyl propionate, ethyl butyrate, ethyl lactate, At least one of ethyl nonanoate, triethyl phosphate, ethyl hexanoate, ethyl formate, ethyl cyclohexanoate, ethyl heptanoate and ethyl cinnamate. Specific examples of the ether-based solvent include, but are not limited to, at least one of methyl ether, diethyl ether, diphenyl ether, ethylene oxide, and tetrahydrofuran.
根据本发明，为了更有利于甲酸根的附着，优选地，所述电解质的pH范围为4～13，更优选为5～11。其中，将所述电解质的pH值调节至上述范围内的方法通常可以为往电解质中加入酸或者碱，具体操作为本领域技术人员公知，在此不作赘述。According to the present invention, in order to further facilitate the attachment of formate, preferably, the pH of the electrolyte ranges from 4 to 13, and more preferably from 5 to 11. The method for adjusting the pH of the electrolyte to the above range may generally include adding an acid or an alkali to the electrolyte. The specific operation is well known to those skilled in the art, and details are not described herein.
所述电化学重构的目的在于使得铜材料的晶面发生重构，使其由原来的(111)或(100)晶面至少部分转化为(110)晶面，从而为后续的电化学沉积奠定良好的基础。所述电化学重构可以采用循环伏安技术、方波伏安技术和差分脉冲伏安技术中的至少一种。所述电化学重构的电化学窗口优选为-5V～5V，更优选为-2V～1V，最优选为-1V～0.5V；扫描速度优选为10 -1～10 3mV/s，更优选为1～10 2mV/s，最优选为5～20mV/s。此外，所述电化学重构的温度优选为-70～200℃，更优选为10～100℃，最优选为室温～60℃。当所述电化学重构采用循环伏安技术时，扫描圈数优选为1～1000圈，更优选为1～100圈，最优选为1～10圈。 The purpose of the electrochemical reconstruction is to restructure the crystal plane of the copper material, so that it is at least partially converted from the original (111) or (100) crystal plane to the (110) crystal plane, so as to facilitate subsequent electrochemical deposition. Lay a good foundation. The electrochemical reconstruction may use at least one of cyclic voltammetry, square wave voltammetry, and differential pulse voltammetry. The electrochemical window of the electrochemical reconstruction is preferably -5V to 5V, more preferably -2V to 1V, and most preferably -1V to 0.5V; the scanning speed is preferably 10 -1 to 10 3 mV / s, and more preferably It is 1 to 10 2 mV / s, and most preferably 5 to 20 mV / s. In addition, the temperature of the electrochemical reconstruction is preferably -70 to 200 ° C, more preferably 10 to 100 ° C, and most preferably room temperature to 60 ° C. When the electrochemical reconstruction uses a cyclic voltammetry technique, the number of scanning cycles is preferably 1 to 1000 cycles, more preferably 1 to 100 cycles, and most preferably 1 to 10 cycles.
所述电化学沉积的目的在于使得电解液中的甲酸根通过电镀方式附着在铜材料的表面。所述电化学沉积可以采用恒电位沉积法、恒电流沉积法和欠电位沉积法中的至少一种。其中，所述恒电位沉积法的电位范围优选为-5V～5V，更优选为-5V～0V，最优选为-2V～0V；所述恒电流沉积法的电流范围优选为10 -3～10 3mA/cm 2，更优选为10 -2～10 2mA/cm 2，最优选为10 -1～10 1mA/cm 2。此外，所述电化学沉积的温度优选为-70～200℃，更优选为0℃～200℃，最优选为室温～60℃；时间优选为0.1～1000min，更优选为1～100min，最优选为5～30min。 The purpose of the electrochemical deposition is to make the formate in the electrolyte adhere to the surface of the copper material by electroplating. The electrochemical deposition may use at least one of a constant potential deposition method, a constant current deposition method, and an underpotential deposition method. Among them, the potential range of the potentiostatic deposition method is preferably -5V to 5V, more preferably -5V to 0V, and most preferably -2V to 0V; the current range of the constant current deposition method is preferably 10 -3 to 10 3 mA / cm 2 , more preferably 10 -2 to 10 2 mA / cm 2 , and most preferably 10 -1 to 10 1 mA / cm 2 . In addition, the temperature of the electrochemical deposition is preferably -70 to 200 ° C, more preferably 0 to 200 ° C, and most preferably room temperature to 60 ° C. The time is preferably 0.1 to 1000min, more preferably 1 to 100min, and most preferably It is 5 to 30 minutes.
此外，所述电化学重构和电化学沉积可以采用密封式，也可以采用开放式，优选采用密封式，这样能够减少外界的干扰。In addition, the electrochemical reconstruction and electrochemical deposition may adopt a sealed type or an open type, preferably a sealed type, so as to reduce external interference.
本发明对所述含铜材料的种类没有特别的限定，可以为现有的各种材质为铜的材料，包括纯铜材料(白铜、黄铜)、铜合金等，具体可以选自铜箔、泡沫铜、铜粉、铜电缆、铜水龙头、铜纳米线和铜电线中的至少一种。The present invention does not specifically limit the type of the copper-containing material, and it can be any existing copper material, including pure copper materials (copper copper, brass), copper alloys, etc., which can be specifically selected from copper foil, At least one of foamed copper, copper powder, copper cable, copper faucet, copper nanowire, and copper wire.
本发明的有益效果如下：The beneficial effects of the present invention are as follows:
1.本发明采用电化学的方法让甲酸根镀在铜材料表面，通过电化学重构和电化学沉积的协同配合作用实现甲酸根的吸附，从而增强了铜材料的抗氧化能力。1. The present invention adopts an electrochemical method to allow formate to be plated on the surface of a copper material, and to achieve the adsorption of formate through the synergistic effect of electrochemical reconstruction and electrochemical deposition, thereby enhancing the oxidation resistance of the copper material.
2.本发明采用电化学处理的铜材料相比处理前具有较强的抗氧化能力(包括抗高温氧化)、耐盐碱腐蚀性和较高的导电性，可用于电线、印刷电路板、电机、变压器、卫浴等领域。2. The electrochemically treated copper material of the present invention has stronger oxidation resistance (including high temperature oxidation resistance), salt and alkali corrosion resistance and higher electrical conductivity than before treatment, and can be used for electric wires, printed circuit boards, and motors. , Transformers, sanitary and other fields.
3.本发明操作简单、条件温和、成本低，在常温下即可实现对各种铜材料的有效抗氧化 防腐蚀处理。3. The invention has simple operation, mild conditions, and low cost, and can achieve effective oxidation and corrosion treatment of various copper materials at normal temperature.
4.由本发明提供的方法处理得到的铜材料具有良好的抗氧化性能，避免使用铅、铬、镉等有潜在毒性的金属或氰化物，符合中华人民共和国环境保护法相关规定。4. The copper material processed by the method provided by the present invention has good oxidation resistance, avoids the use of potentially toxic metals such as lead, chromium, cadmium or cyanide, and complies with the relevant provisions of the Environmental Protection Law of the People's Republic of China.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例1中未修饰铜箔在0.1M的NaOH溶液中室温放置10h的SEM图，说明未经修饰的铜箔很容易被氧化腐蚀，从而表面变得粗糙。FIG. 1 is an SEM image of the unmodified copper foil in Example 1 placed in a 0.1M NaOH solution at room temperature for 10 hours, indicating that the unmodified copper foil is easily oxidized and corroded, and the surface becomes rough.
图2为实施例1中甲酸根修饰铜箔在0.1M的NaOH溶液中室温放置10h的SEM图，说明经过甲酸盐修饰后铜箔表面仍光滑平整，抗氧化性明显增强。FIG. 2 is an SEM image of the formate-modified copper foil in Example 1 placed at room temperature in a 0.1M NaOH solution for 10 hours at room temperature, which shows that the surface of the copper foil after the formate modification is still smooth and flat, and the oxidation resistance is significantly enhanced.
图3为实施例7中未修饰镀层铜在3wt％的NaCl溶液中室温放置24h的光学照片，说明未经修饰的镀层铜易被氧化腐蚀，表面暗淡。FIG. 3 is an optical photograph of the unmodified plated copper in Example 7 which is left at room temperature for 24 h in a 3 wt% NaCl solution, which illustrates that the unmodified plated copper is easily oxidized and corroded, and the surface is dull.
图4为实施例7中甲酸根修饰镀层铜在3wt％的NaCl溶液中室温放置10h的光学照片，说明经过甲酸盐修饰后铜箔表面仍光滑平整、颜色均匀，抗氧化性明显增强。FIG. 4 is an optical photo of the formate-modified copper plated in Example 7 placed at room temperature for 10 hours in a 3% by weight NaCl solution, illustrating that the surface of the copper foil after the formate modification is still smooth, uniform in color, and the oxidation resistance is significantly enhanced.
图5为实施例8中电化学重构镀层铜前后的x-射线衍射谱图，经过电化学重构后的镀层铜的(110)晶面的峰明显增强，说明甲酸根已经诱导铜表面发生了重构。FIG. 5 is an x-ray diffraction spectrum of the copper before and after electrochemical reconstruction of the coated copper in Example 8. The peak of the (110) crystal plane of the copper after the electrochemical reconstruction is significantly enhanced, indicating that formate has induced copper surface occurrence. Refactored.
具体实施方式detailed description
下面详细描述本发明的实施例，所述实施例的示例旨在用于解释本发明，而不能理解为对本发明的限制。实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。The embodiments of the present invention are described in detail below, and the examples of the embodiments are intended to explain the present invention, but should not be construed as limiting the present invention. If the specific technology or condition is not indicated in the examples, the technology or condition described in the literature in the art or the product description is performed. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that are commercially available.
实施例1：Example 1:
取1×3cm 2铜箔(厚度：25μm)，用1wt％甲酸的乙醇溶液超声洗涤表面的有机物和氧化物，再用乙醇洗涤后，氮气吹干备用。采用CHI660E的电化学工作站作为电化学处理的设备，将清洗后的铜箔作为工作电极，饱和甘汞电极作为参比电极，铂片电极作为对电极，构成三电极体系，采用1wt％的甲酸钠水溶液(pH＝10)作为电解质溶液，采用循环伏安技术(扫描速度：10mV/s，扫描范围：-1～0.5V)于30℃下对铜箔表面扫描2次，以对铜箔表面进行电化学重构，将电化学重构前后的铜箔进行x-射线衍射测试，结果表明，经过电化学重构后的铜箔的(110)晶面的x-射线衍射峰明显增强，说明甲酸根诱导铜表面发生了重构。然后在室温下，-0.84V的恒电位电化学沉积30min，即可得到抗氧化处理的铜箔。图1为未修饰铜 箔在0.1M的NaOH溶液中室温放置10h的SEM图，说明未经修饰的铜箔很容易被氧化腐蚀，从而表面变得粗糙；图2为甲酸根修饰铜箔在0.1M的NaOH溶液中室温放置10h的SEM图，说明经过甲酸盐修饰后铜箔表面光滑平整，抗氧化性明显增强。 Take 1 × 3 cm 2 copper foil (thickness: 25 μm), ultrasonically wash the surface organic matter and oxide with a 1% by weight formic acid ethanol solution, and then wash with ethanol, then blow dry with nitrogen for use. A CHI660E electrochemical workstation is used as the electrochemical treatment equipment. The cleaned copper foil is used as the working electrode, the saturated calomel electrode is used as the reference electrode, and the platinum sheet electrode is used as the counter electrode to form a three-electrode system. A 1 wt% sodium formate aqueous solution is used. (pH = 10) As an electrolyte solution, a cyclic voltammetry technique (scanning speed: 10 mV / s, scanning range: -1 to 0.5 V) was used to scan the surface of the copper foil twice at 30 ° C. to electrically conduct the surface of the copper foil. Chemical reconstruction. The copper foil before and after electrochemical reconstruction was subjected to x-ray diffraction test. The results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that formate Induction of copper surface reconstruction. Then, at room temperature, a constant potential electrochemical deposition of -0.84V for 30 min can obtain an anti-oxidation copper foil. Figure 1 is an SEM image of unmodified copper foil placed in a 0.1M NaOH solution at room temperature for 10 hours, indicating that the unmodified copper foil is easily oxidized and corroded, so that the surface becomes rough; Figure 2 is formate modified copper foil at 0.1 The SEM image of M in NaOH solution at room temperature for 10 hours shows that the surface of the copper foil is smooth and flat, and the oxidation resistance is significantly enhanced after formate modification.
实施例2：Example 2:
取1×3cm 2铜箔(厚度：25μm)，用1wt％的甲酸水溶液超声10min来洗涤表面的有机物和氧化物，再用乙醇洗涤后，氮气吹干备用。以CHI440E的电化学工作站作为电化学处理的设备，将洗净后的铜箔作为工作电极，饱和甘汞电极作为参比电极，石墨片作为对电极，构成三电极体系，采用1wt％的甲酸钠/乙二醇溶液(pH＝9)作为电解质溶液，先采用循环伏安技术(扫描速度：50mV/s，扫描范围：-1.5～0.5V)于45℃下对铜箔表面扫描2次，以对铜箔表面进行电化学重构，将电化学重构前后的铜箔进行x-射线衍射测试，结果表明，经过电化学重构后的铜箔的(110)晶面的x-射线衍射峰明显增强，说明甲酸根诱导铜表面发生了重构。然后在室温下，以-0.78V的恒电位电化学沉积10min，采用乙醇洗涤，氮气吹干，即可得到抗氧化处理的铜箔，将处理前后的铜箔在0.1M的NaOH溶液中室温放置10h之后分别进行SEM测试，结果显示经过甲酸盐修饰后的铜箔表面光滑平整，可见其抗氧化性得以了提高。 Take 1 × 3 cm 2 copper foil (thickness: 25 μm), ultrasonically wash the surface organic matter and oxides with a 1 wt% formic acid aqueous solution for 10 minutes, and then wash with ethanol, then blow dry with nitrogen for use. CHI440E's electrochemical workstation is used as the electrochemical treatment equipment. The washed copper foil is used as the working electrode, the saturated calomel electrode is used as the reference electrode, and the graphite sheet is used as the counter electrode to form a three-electrode system. 1wt% sodium formate / Glycol solution (pH = 9) was used as the electrolyte solution. Cyclic voltammetry (scanning speed: 50mV / s, scanning range: -1.5 ～ 0.5V) was used to scan the surface of copper foil twice at 45 ° C. The surface of the copper foil was electrochemically reconstructed. The copper foil before and after the electrochemical reconstruction was subjected to an x-ray diffraction test. The results showed that the (110) crystal plane of the copper foil after the electrochemical reconstruction had obvious x-ray diffraction peaks. The enhancement indicates that formate induces remodeling of the copper surface. Then at room temperature, electrochemical deposition at a constant potential of -0.78V for 10 min, washing with ethanol, and blowing dry with nitrogen to obtain an anti-oxidation copper foil, the copper foil before and after the treatment was placed in a 0.1M NaOH solution at room temperature After 10 hours, the SEM tests were performed. The results showed that the surface of the copper foil after formate modification was smooth and flat, and its oxidation resistance was improved.
实施例3：Example 3:
取1×3cm 2的铜箔1片，用1wt％的甲酸水溶液超声10min来洗涤表面的有机物和氧化物，再用乙醇洗涤后，氮气吹干备用。以CHI440E的电化学工作站作为电化学处理的设备，将洗净后的铜箔作为工作电极，饱和甘汞电极作为参比电极，石墨片电极作为对电极，采用2wt％的甲酸钠水溶液作为电解质溶液，先采用循环伏安技术(扫描速度：50mV/s，扫描范围：-1.5～0.5V)于30℃下对铜箔表面扫描2次，以对铜箔表面进行电化学重构，将电化学重构前后的铜箔进行x-射线衍射测试，结果表明，经过电化学重构后的铜箔的(110)晶面的x-射线衍射峰明显增强，说明甲酸根诱导铜表面发生了重构。然后在室温下，以-0.73V的恒电位电化学沉积10min，采用乙醇洗涤，氮气吹干，即可得到抗氧化处理的铜箔，将处理前后的铜箔分别在0.1M的NaOH溶液中室温放置10h之后进行SEM测试，结果表明经过甲酸盐修饰后的铜箔具有更光滑平整的表面，可见其抗氧化性得以了提高。 Take 1 piece of copper foil of 1 × 3 cm 2 , ultrasonically wash the surface organic matters and oxides with a 1 wt% formic acid aqueous solution for 10 minutes, and then wash with ethanol, then blow dry with nitrogen for use. The electrochemical workstation of CHI440E was used as the electrochemical treatment equipment, the washed copper foil was used as the working electrode, the saturated calomel electrode was used as the reference electrode, the graphite sheet electrode was used as the counter electrode, and the 2wt% sodium formate aqueous solution was used as the electrolyte solution. First, the cyclic voltammetry technology (scanning speed: 50mV / s, scanning range: -1.5 to 0.5V) was used to scan the copper foil surface twice at 30 ° C to perform electrochemical reconstruction of the copper foil surface and the electrochemical weight was changed. X-ray diffraction tests were performed on the copper foil before and after the formation, and the results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that formate induced copper surface reconstruction. Then at room temperature, electrochemical deposition at a constant potential of -0.73V for 10 min, washing with ethanol, and blowing dry with nitrogen to obtain an anti-oxidation copper foil, the copper foils before and after the treatment were each in a 0.1M NaOH solution at room temperature After 10 hours of SEM testing, the results show that the copper foil after formate modification has a smoother and smoother surface, showing that its oxidation resistance has been improved.
实施例4：Example 4:
取5×10cm 2的铜箔1片，用3wt％的甲酸乙醇溶液超声5min来洗涤表面的有机物和氧 化物，再用乙醇洗涤后，氮气吹干备用。以CHI660E的电化学工作站作为电化学处理的设备，将洗净后的铜箔作为工作电极，饱和甘汞电极作为参比电极，石墨片作为对电极，构成三电极体系，采用2wt％的甲酸钠水溶液(pH＝8)作为电解质溶液，先采用循环伏安技术(扫描速度：100mV/s，扫描范围：-1.5～0.5V)于60℃下对铜箔表面扫描1次，以对铜箔表面进行电化学重构，将电化学重构前后的铜箔进行x-射线衍射测试，结果表明，经过电化学重构后的铜箔的(110)晶面的x-射线衍射峰明显增强，说明甲酸根诱导铜表面发生了重构。然后在室温下，采用电流阶跃技术以-0.65V的恒电位电化学沉积8min，采用乙醇洗涤，氮气吹干，即可得到抗氧化处理的铜箔，将处理前后的铜箔分别在0.1M的NaOH溶液中室温放置10h之后进行SEM测试，结果表明经过甲酸盐修饰后的铜箔具有更光滑平整的表面，可见其抗氧化性得以了提高。 Take 1 piece of copper foil of 5 × 10 cm 2 and ultrasonically wash the surface organic matter and oxides with a 3 wt% formic acid ethanol solution for 5 minutes. After washing with ethanol, it is blown with nitrogen for use. The electrochemical workstation of CHI660E was used as the electrochemical treatment equipment. The washed copper foil was used as the working electrode, the saturated calomel electrode was used as the reference electrode, and the graphite sheet was used as the counter electrode to form a three-electrode system. A 2 wt% sodium formate aqueous solution was used. (pH = 8) As the electrolyte solution, the cyclic voltammetry technique (scanning speed: 100mV / s, scanning range: -1.5 to 0.5V) was used to scan the surface of the copper foil once at 60 ° C to perform the analysis on the surface of the copper foil. Electrochemical reconstruction. The copper foil before and after electrochemical reconstruction was subjected to x-ray diffraction testing. The results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that formic acid The root induced copper surface reconstruction. Then at room temperature, the current step technology was used for electrochemical deposition at a constant potential of -0.65V for 8 minutes, washed with ethanol, and blown with nitrogen to obtain an anti-oxidation copper foil. The copper foil before and after the treatment was 0.1M. The SEM test was performed after leaving the solution in NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
实施例5：Example 5:
取2×6cm 2的铜箔1片，用2wt％的甲酸乙醇溶液超声10min来洗涤表面的有机物和氧化物，再用乙醇洗涤后，氮气吹干备用。将洗净后的铜箔作为工作电极，饱和甘汞电极作为参比电极，铂片电极作为对电极，构成三电极体系，在2wt％的甲酸钠水溶液(pH＝11)中，扫循环伏安曲线(扫描速度：10mV/s，扫描范围：-0.8～0.3V)于10℃下对铜箔表面扫描2次，以对铜箔表面进行电化学重构，将电化学重构前后的铜箔进行x-射线衍射测试，结果表明，经过电化学重构后的铜箔的(110)晶面的x-射线衍射峰明显增强，说明甲酸根诱导铜表面发生了重构。随后在60℃水浴条件下，采用电流阶跃技术以-0.63V的恒电位电化学沉积20min，采用乙醇/H 2O混合溶剂洗涤，氮气吹干，即可得到抗氧化处理的铜箔，将处理前后的铜箔在0.1M的NaOH溶液中室温放置10h之后分别进行SEM测试，结果表明经过甲酸盐修饰后的铜箔具有更光滑平整的表面，可见其抗氧化性得以了提高。 Take 2 pieces of 2 × 6cm 2 copper foil, ultrasonically wash the surface organic matter and oxide with 2wt% formic acid ethanol solution for 10min, and then wash with ethanol, then blow dry with nitrogen for use. The washed copper foil was used as the working electrode, the saturated calomel electrode was used as the reference electrode, and the platinum sheet electrode was used as the counter electrode to form a three-electrode system. The cyclic voltammetry curve was scanned in a 2 wt% sodium formate aqueous solution (pH = 11). (Scanning speed: 10mV / s, scanning range: -0.8 to 0.3V) Scan the copper foil surface twice at 10 ° C to perform electrochemical reconstruction of the copper foil surface, and perform copper foil before and after electrochemical reconstruction. The x-ray diffraction test showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that formate induced the reconstruction of the copper surface. Subsequently, in a 60 ° C water bath condition, the current step technology was used for electrochemical deposition at a constant potential of -0.63V for 20 min, washed with a mixed solvent of ethanol / H 2 O, and blown with nitrogen to obtain an oxidation-resistant copper foil. The copper foil before and after the treatment was placed in a 0.1M NaOH solution at room temperature for 10 hours and then subjected to SEM tests. The results showed that the formate-modified copper foil had a smoother and smoother surface, and its oxidation resistance was improved.
实施例6：Example 6:
取2×6cm 2的铜箔1片，在2wt％的甲酸乙醇溶液中超声10min，洗涤表面的有机物和氧化物，再用乙醇洗涤后，氮气吹干备用。将洗净后的铜箔作为工作电极，银/氯化银电极作为参比电极，石磨棒电极作为对电极，构成三电极体系，在5wt％的甲酸钠水溶液(pH＝7)中，扫循环伏安曲线(扫描速度：20mV/s，扫描范围：-1.2～0.5V)于20℃下对铜箔表面扫描2次，以对铜箔表面进行电化学重构，将电化学重构前后的铜箔进行x-射线衍射测试，结果表明，经过电化学重构后的铜箔的(110)晶面的x-射线衍射峰明显增强，说明甲酸根诱导铜表面发生了重构。随后在40℃水浴条件下，采用电流阶跃技术以-0.68V的恒电位电化学沉积 15min，采用乙醇/H 2O混合溶剂洗涤，氮气吹干，即可得到抗氧化处理的铜箔，将处理前后的铜箔在0.1M的NaOH溶液中室温放置10h之后分别进行SEM测试，结果表明经过甲酸盐修饰后的铜箔具有更光滑平整的表面，可见其抗氧化性得以了提高。 Take 1 piece of 2 × 6cm 2 copper foil, ultrasonicate it in a 2wt% formic acid ethanol solution for 10min, wash the organics and oxides on the surface, wash with ethanol, and blow dry with nitrogen for use. The washed copper foil was used as the working electrode, the silver / silver chloride electrode was used as the reference electrode, and the stone mill rod electrode was used as the counter electrode to form a three-electrode system. In a 5 wt% sodium formate aqueous solution (pH = 7), the cycle was swept Voltammetry curve (scan speed: 20mV / s, scan range: -1.2 ～ 0.5V) Scan the copper foil surface twice at 20 ℃ to perform electrochemical reconstruction of the copper foil surface. The x-ray diffraction test of the copper foil showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil was significantly enhanced after electrochemical reconstruction, indicating that formate induced the reconstruction of the copper surface. Subsequently, under a 40 ° C water bath condition, a current step technology was used for electrochemical deposition at a constant potential of -0.68V for 15 minutes, and the mixture was washed with a mixed solvent of ethanol / H 2 O and dried with nitrogen to obtain an anti-oxidation copper foil. The copper foil before and after the treatment was placed in a 0.1M NaOH solution at room temperature for 10 hours and then subjected to SEM tests. The results showed that the formate-modified copper foil had a smoother and smoother surface, and its oxidation resistance was improved.
实施例7：Example 7:
取5×2cm 2商业铜镀物件，镀层厚度为2μm，在60℃采用CHI 440c的电化学工作站作为电化学处理设备，将镀层物件作为工作电极，饱和甘汞电极作为参比电极，玻碳电极作为对电极，构成三电极体系，采用5wt％的甲酸钠水溶液(pH＝10)作为电解质溶液，采用循环伏安(扫描速度：10mV/s，扫描范围：-0.8～0.2V)于5℃下对镀层铜扫描2次，以对镀层铜表面进行电化学重构，将电化学重构前后的铜箔进行x-射线衍射测试，结果表明，经过电化学重构后的铜箔的(110)晶面的x-射线衍射峰明显增强，说明甲酸根诱导铜表面发生了重构。随后在50℃下用-0.66V的恒电位电化学沉积10min，即可得到抗氧化处理的镀层铜，0.1M NaCl溶液中放置24h。 Take 5 × 2cm 2 commercial copper-plated objects with a coating thickness of 2 μm. At 60 ° C, an electrochemical workstation CHI 440c is used as the electrochemical processing equipment. The coated objects are used as working electrodes, saturated calomel electrodes are used as reference electrodes, and glassy carbon electrodes are used. As a counter electrode, a three-electrode system was constructed, and a 5 wt% sodium formate aqueous solution (pH = 10) was used as an electrolyte solution. Cyclic voltammetry (scanning speed: 10 mV / s, scanning range: -0.8 to 0.2 V) was used at 5 ° C. The coated copper was scanned twice to perform electrochemical reconstruction of the coated copper surface. The copper foil before and after the electrochemical reconstruction was subjected to an x-ray diffraction test. The results showed that the (110) crystal of the copper foil after the electrochemical reconstruction was The X-ray diffraction peaks on the surface were significantly enhanced, indicating that formate induced the reconstruction of the copper surface. Subsequently, at a temperature of 50 ° C. and a constant potential of -0.66 V for electrochemical deposition for 10 min, an anti-oxidation coated copper can be obtained, which is left in a 0.1 M NaCl solution for 24 h.
图3为未修饰镀层铜室温0.1M的NaCl溶液中放置24h的光学照片，说明未经修饰的镀层铜易氧化腐蚀，从而表面氧化；图4为甲酸根修饰镀层铜室温0.1M的NaCl溶液中放置10h的光学照片，说明经过甲酸盐修饰后铜箔表面光滑平整，抗氧化性明显增强。Figure 3 is an optical photo of unmodified copper plated at room temperature in a 0.1M NaCl solution for 24 hours, illustrating that the unmodified copper plated is susceptible to oxidative corrosion and thus surface oxidation; Figure 4 is a formate modified copper plated at 0.1M NaCl solution at room temperature The optical photo that was left for 10 hours showed that the surface of the copper foil was smooth and flat, and the oxidation resistance was significantly enhanced after formate modification.
实施例8：Example 8:
取5×2cm 2商业铜镀物件，镀层厚度为2μm，在40℃采用CHI 440c的电化学工作站作为电化学处理设备，将镀层物件作为工作电极，饱和甘汞电极作为参比电极，玻碳电极作为对电极，构成三电极体系，采用1wt％的甲酸钠水溶液(pH＝10)作为电解质溶液，采用循环伏安(扫描速度：10mV/s，扫描范围：-0.8～0.2V)于75℃下对镀层铜扫描2次，以对镀层铜表面进行电化学重构，电化学重构镀层铜前后的x-射线衍射谱图如图5所示。从图5的结果可以看出，经过电化学重构后的镀层铜的(110)晶面的x-射线衍射峰明显增强，说明甲酸根诱导铜表面发生了重构。随后在40℃下用-0.6V的恒电位电化学沉积10min，即可得到抗氧化处理的镀层铜，将处理前后的镀层铜在0.1M的NaOH溶液中室温放置10h之后分别进行SEM测试，结果表明经过甲酸盐修饰后的镀层铜有更光滑平整的表面，可见其抗氧化性得以了提高。 Take 5 × 2cm 2 commercial copper-plated objects with a coating thickness of 2μm, and use a CHI 440c electrochemical workstation as an electrochemical treatment device at 40 ° C. Use the coated objects as working electrodes, saturated calomel electrodes as reference electrodes, and glassy carbon electrodes. As a counter electrode, a three-electrode system was constructed, and a 1 wt% sodium formate aqueous solution (pH = 10) was used as an electrolyte solution, and cyclic voltammetry (scanning speed: 10 mV / s, scanning range: -0.8 to 0.2 V) was used at 75 ° C. The coating copper was scanned twice to electrochemically reconstruct the surface of the coated copper. The x-ray diffraction spectra before and after the electrochemical reconstruction of the coated copper are shown in FIG. 5. It can be seen from the results in FIG. 5 that the x-ray diffraction peak of the (110) crystal plane of the plated copper after electrochemical reconstruction is significantly enhanced, indicating that formate-induced copper surface reconstruction has occurred. Subsequent electrochemical deposition at 40 ° C with a constant potential of -0.6V for 10 min can obtain anti-oxidation coated copper. The copper before and after the treatment was placed in a 0.1M NaOH solution at room temperature for 10 hours and then subjected to SEM tests. Results It shows that the formate-modified copper has a smoother and smoother surface, and it can be seen that its oxidation resistance is improved.
实施例9：Example 9:
步骤一：表面清洗。取长3cm、宽1cm、厚25μm的铜箔，放置于1wt％甲酸的乙醇溶 液中，超声5min洗涤去除表面有机物和氧化物，氮气吹扫干燥。Step 1: Surface cleaning. A copper foil with a length of 3 cm, a width of 1 cm, and a thickness of 25 m was placed in an ethanol solution of 1 wt% formic acid, washed with ultrasound for 5 minutes to remove surface organics and oxides, and dried by nitrogen purging.
步骤二：电化学重构和电化学沉积。Step two: electrochemical reconstruction and electrochemical deposition.
(1)将清洗干燥后的铜箔作为工作电极，饱和甘汞电极为参比电极，铂片电极作为对电极；(1) Use the cleaned and dried copper foil as the working electrode, the saturated calomel electrode as the reference electrode, and the platinum sheet electrode as the counter electrode;
(2)电解质溶液：配制1wt％的甲酸钠水溶液，调节溶液的pH为9；(2) Electrolyte solution: prepare a 1 wt% sodium formate aqueous solution, and adjust the pH of the solution to 9;
(3)循环伏安技术：扫描速度：10mV/s，扫描范围：-1V至0.5V，于25℃下对铜箔表面扫描2次，以对铜箔表面进行重构，将电化学重构前后的铜箔进行x-射线衍射测试，结果表明，经过电化学重构后的铜箔的(110)晶面的x-射线衍射峰明显增强，说明甲酸根诱导铜表面发生了重构；(3) Cyclic voltammetry technology: scanning speed: 10mV / s, scanning range: -1V to 0.5V, scan the copper foil surface twice at 25 ° C to reconstruct the copper foil surface and reconstruct the electrochemical reconstruction X-ray diffraction tests were performed on the copper foil before and after. The results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that formate induced the reconstruction of the copper surface;
(4)恒电位电化学沉积：室温，恒电位-0.73V，沉积时间30min。(4) potentiostatic electrochemical deposition: room temperature, potentiostatic -0.73V, deposition time 30min.
步骤三：乙醇清洗，干燥。Step 3: Wash with ethanol and dry.
将处理前后的铜箔在0.1M的NaOH溶液中室温放置10h之后分别进行SEM测试，结果表明经过甲酸盐修饰后的铜箔具有更光滑平整的表面，可见其抗氧化性得以了提高。The SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
实施例10：Example 10:
步骤一：表面清洗。取长4cm、宽2cm、厚30μm的铜箔，放置于1.5％甲酸的乙醇溶液中，超声3min洗涤去除表面有机物和氧化物，氮气吹扫干燥。Step 1: Surface cleaning. A copper foil with a length of 4 cm, a width of 2 cm, and a thickness of 30 μm was placed in an ethanol solution of 1.5% formic acid, and the surface organic matter and oxides were removed by ultrasonic washing for 3 min, and then dried by nitrogen purging.
步骤二：电化学重构和电化学沉积。Step two: electrochemical reconstruction and electrochemical deposition.
(1)将清洗干燥后的铜箔作为工作电极，饱和甘汞电极为参比电极，铂片电极作为对电极；(1) Use the cleaned and dried copper foil as the working electrode, the saturated calomel electrode as the reference electrode, and the platinum sheet electrode as the counter electrode;
(2)电解质溶液：配制2wt％的甲酸钠水溶液，调节溶液的pH为10；(2) Electrolyte solution: prepare a 2 wt% sodium formate aqueous solution and adjust the pH of the solution to 10;
(3)循环伏安技术：扫描速度：10mV/s，扫描范围：-1V至0.5V，于35℃下对铜箔表面扫描2次，以对铜箔表面进行重构，将电化学重构前后的铜箔进行x-射线衍射测试，结果表明，经过电化学重构后的铜箔的(110)晶面的x-射线衍射峰明显增强，说明甲酸根诱导铜表面发生了重构；(3) Cyclic voltammetry: scanning speed: 10mV / s, scanning range: -1V to 0.5V, scan the copper foil surface twice at 35 ° C to reconstruct the copper foil surface and reconstruct the electrochemical X-ray diffraction tests were performed on the copper foil before and after, and the results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that formate induced the reconstruction of the copper surface;
(4)恒电位电化学沉积：室温，恒电位-0.69V，沉积时间30min。(4) potentiostatic electrochemical deposition: room temperature, potentiostatic -0.69V, deposition time 30min.
步骤三：乙醇清洗，干燥。Step 3: Wash with ethanol and dry.
将处理前后的铜箔在0.1M的NaOH溶液中室温放置10h之后分别进行SEM测试，结果表明经过甲酸盐修饰后的铜箔具有更光滑平整的表面，可见其抗氧化性得以了提高。The SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
实施例11：Example 11:
步骤一：表面清洗。取长3cm、宽0.5cm、厚20μm的铜箔，放置于0.5wt％甲酸的乙醇溶液中，超声8min洗涤去除表面有机物和氧化物，氮气吹扫干燥。Step 1: Surface cleaning. A copper foil with a length of 3 cm, a width of 0.5 cm, and a thickness of 20 μm was placed in a 0.5 wt% formic acid in ethanol solution, ultrasonically washed for 8 minutes to remove surface organics and oxides, and dried by nitrogen purging.
步骤二：电化学重构和电化学沉积。Step two: electrochemical reconstruction and electrochemical deposition.
(1)将清洗干燥后的铜箔作为工作电极，饱和甘汞电极为参比电极，铂片电极作为对电极；(1) Use the cleaned and dried copper foil as the working electrode, the saturated calomel electrode as the reference electrode, and the platinum sheet electrode as the counter electrode;
(2)电解质溶液：配制5wt％的甲酸钠水溶液，调节溶液的pH为8；(2) Electrolyte solution: prepare a 5 wt% sodium formate aqueous solution and adjust the pH of the solution to 8;
(3)循环伏安技术：扫描速度：10mV/s，扫描范围：-1V至0.5V，于15℃下对铜箔表面扫描2次，以对铜箔表面进行重构，将电化学重构前后的铜箔进行x-射线衍射测试，结果表明，经过电化学重构后的铜箔的(110)晶面的x-射线衍射峰明显增强，说明甲酸根诱导铜表面发生了重构；(3) Cyclic voltammetry: scanning speed: 10mV / s, scanning range: -1V to 0.5V, scan the copper foil surface twice at 15 ° C to reconstruct the surface of the copper foil and reconstruct the electrochemical X-ray diffraction tests were performed on the copper foil before and after, and the results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that formate induced the reconstruction of the copper surface;
(4)恒电位电化学沉积：室温，恒电位-0.62V，沉积时间30min；(4) potentiostatic electrochemical deposition: room temperature, potentiostatic -0.62V, deposition time 30min;
步骤三：乙醇清洗，干燥。Step 3: Wash with ethanol and dry.
将处理前后的铜箔在0.1M的NaOH溶液中室温放置10h之后分别进行SEM测试，结果表明经过甲酸盐修饰后的铜箔具有更光滑平整的表面，可见其抗氧化性得以了提高。The SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
实施例12：Example 12:
步骤一：表面清洗。取长5cm、宽3cm、厚40μm的铜箔，放置于2wt％甲酸的乙醇溶液中，超声1min洗涤去除表面有机物和氧化物，氮气吹扫干燥。Step 1: Surface cleaning. A 5 cm long, 3 cm wide and 40 μm thick copper foil was taken and placed in a 2 wt% formic acid in ethanol solution, and the surface organic matter and oxides were removed by ultrasonic cleaning for 1 min, and then dried by nitrogen purging.
步骤二：电化学重构和电化学沉积。Step two: electrochemical reconstruction and electrochemical deposition.
(1)将清洗干燥后的铜箔作为工作电极，饱和甘汞电极为参比电极，铂片电极作为对电极；(1) Use the cleaned and dried copper foil as the working electrode, the saturated calomel electrode as the reference electrode, and the platinum sheet electrode as the counter electrode;
(2)电解质溶液：配制10wt％的甲酸钠水溶液，调节溶液的pH为10；(2) Electrolyte solution: prepare a 10 wt% sodium formate aqueous solution, and adjust the pH of the solution to 10;
(3)循环伏安技术：扫描速度：10mV/s，扫描范围：-1V至0.5V，于5℃下对铜箔表面扫描2次，以对铜箔表面进行重构，将电化学重构前后的铜箔进行x-射线衍射测试，结果表明，经过电化学重构后的铜箔的(110)晶面的x-射线衍射峰明显增强，说明甲酸根诱导铜表面发生了重构；(3) Cyclic voltammetry: scanning speed: 10mV / s, scanning range: -1V to 0.5V, scanning the copper foil surface twice at 5 ° C to reconstruct the copper foil surface and electrochemical reconstruction X-ray diffraction tests were performed on the copper foil before and after, and the results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that formate induced the reconstruction of the copper surface;
(4)恒电位电化学沉积：室温，恒电位-0.54V，沉积时间30min；(4) potentiostatic electrochemical deposition: room temperature, potentiostatic -0.54V, deposition time 30min;
步骤三：乙醇清洗，干燥。Step 3: Wash with ethanol and dry.
将处理前后的铜箔在0.1M的NaOH溶液中室温放置10h之后分别进行SEM测试，结果表明经过甲酸盐修饰后的铜箔具有更光滑平整的表面，可见其抗氧化性得以了提高。The SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
实施例13：Example 13:
步骤一：表面清洗：取25μm厚铜箔，裁成1cm×3cm长方形大小，浸泡在含1wt％甲酸的乙醇溶液中，并超声处理5min，洗去表面残留的有机物和氧化物，再用乙醇超声冲洗3次，氮气吹扫干燥。Step 1: Surface cleaning: take 25μm thick copper foil, cut into 1cm × 3cm rectangular size, soak it in ethanol solution containing 1wt% formic acid, and sonicate for 5min, wash away the remaining organics and oxides on the surface, and then sonicate with ethanol Rinse 3 times and dry with a nitrogen purge.
步骤二：电解液配制：干燥后的铜箔作为工作电极，饱和的甘汞电极为参比电极，铂片电极作为对电极。溶剂为水，同时加入1wt％的甲酸钠水溶液(pH＝10)作为电解质溶液。Step 2: electrolyte preparation: the dried copper foil is used as the working electrode, the saturated calomel electrode is used as the reference electrode, and the platinum sheet electrode is used as the counter electrode. The solvent was water, and at the same time, a 1 wt% aqueous sodium formate solution (pH = 10) was added as an electrolyte solution.
步骤三：电化学重构和电化学沉积：在室温下，采用循环伏安技术(扫描速度：10mV/s，扫描范围：-1～0.5V)，于45℃下进行1个循环的扫描进行重构，将电化学重构前后的铜箔进行x-射线衍射测试，结果表明，经过电化学重构后的铜箔的(110)晶面的x-射线衍射峰明显增强，说明甲酸根诱导铜表面发生了重构；之后在-0.4V的恒电位电化学沉积30min，即可得到抗氧化处理的铜箔。Step 3: Electrochemical reconstruction and electrochemical deposition: At room temperature, using cyclic voltammetry (scanning speed: 10mV / s, scanning range: -1 to 0.5V), perform a scanning cycle at 45 ° C. Reconstruction. The copper foil before and after electrochemical reconstruction was subjected to x-ray diffraction test. The results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that the formate induced The copper surface was reconstituted; afterwards, it was deposited at a constant potential of -0.4V for 30 min to obtain an anti-oxidation copper foil.
步骤四：乙醇清洗，干燥。Step 4: Wash with ethanol and dry.
将处理前后的铜箔在0.1M的NaOH溶液中室温放置10h之后分别进行SEM测试，结果表明经过甲酸盐修饰后的铜箔具有更光滑平整的表面，可见其抗氧化性得以了提高。The SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
实施例14：Example 14:
步骤一：表面清洗：取25μm厚铜箔，裁成1cm×3cm长方形大小，浸泡在含1wt％甲酸的乙醇溶液中，并超声处理5min，洗去表面残留的有机物和氧化物，再用乙醇超声冲洗3次，氮气吹扫干燥。Step 1: Surface cleaning: take 25μm thick copper foil, cut into 1cm × 3cm rectangular size, soak it in ethanol solution containing 1wt% formic acid, and sonicate for 5min, wash away the remaining organics and oxides on the surface, and then sonicate with ethanol Rinse 3 times and dry with a nitrogen purge.
步骤二：电解液配制：干燥后的铜箔作为工作电极，饱和的甘汞电极为参比电极，铂片电极作为对电极。溶剂为水与乙二醇1:1混合，同时加入1wt％的甲酸钠水溶液(pH＝10)作为电解质溶液。Step 2: electrolyte preparation: the dried copper foil is used as the working electrode, the saturated calomel electrode is used as the reference electrode, and the platinum sheet electrode is used as the counter electrode. The solvent was a 1: 1 mixture of water and ethylene glycol, and at the same time, a 1 wt% sodium formate aqueous solution (pH = 10) was added as an electrolyte solution.
步骤三：电化学重构和电化学沉积：在室温下，采用循环伏安技术(扫描速度：10mV/s，扫描范围：-1～0.5V)，于55℃下进行1个循环的扫描进行重构，将电化学重构前后的铜箔进行x-射线衍射测试，结果表明，经过电化学重构后的铜箔的(110)晶面的x-射线衍射峰明显增强，说明甲酸根诱导铜表面发生了重构；之后在-1.0V的恒电位电化学沉积30min，即可得到抗氧化处理的铜箔。Step 3: Electrochemical reconstruction and electrochemical deposition: At room temperature, using cyclic voltammetry (scanning speed: 10mV / s, scanning range: -1 to 0.5V), perform a scanning cycle at 55 ° C. Reconstruction. The copper foil before and after electrochemical reconstruction was subjected to x-ray diffraction test. The results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that the formate induced The copper surface was restructured; afterwards, it was deposited at a constant potential of -1.0V for 30 minutes to obtain an anti-oxidation copper foil.
步骤四：乙醇清洗，干燥。Step 4: Wash with ethanol and dry.
将处理前后的铜箔在0.1M的NaOH溶液中室温放置10h之后分别进行SEM测试，结果表明经过甲酸盐修饰后的铜箔具有更光滑平整的表面，可见其抗氧化性得以了提高。The SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
实施例15：Example 15:
步骤一：表面清洗：取25μm厚铜箔，裁成1×3cm 2长方形大小，浸泡在含1wt％甲酸的乙醇溶液中，并超声处理5min，洗去表面残留的有机物和氧化物，再用乙醇超声冲洗3次，氮气吹扫干燥。 Step 1: Surface cleaning: take 25μm thick copper foil, cut into 1 × 3cm 2 rectangles, soak it in an ethanol solution containing 1wt% formic acid, and sonicate for 5min, wash away the remaining organic matter and oxides on the surface, and then use ethanol Sonicate 3 times and dry with a nitrogen purge.
步骤二：电解液配制：干燥后的铜箔作为工作电极，饱和的甘汞电极为参比电极，铂片电极作为对电极。溶剂为乙二醇，同时加入1％的甲酸钠水溶液(pH＝10)作为电解质溶液。Step 2: electrolyte preparation: the dried copper foil is used as the working electrode, the saturated calomel electrode is used as the reference electrode, and the platinum sheet electrode is used as the counter electrode. The solvent was ethylene glycol, and a 1% aqueous sodium formate solution (pH = 10) was added as an electrolyte solution.
步骤三：电化学重构和电化学沉积：在室温下，采用循环伏安技术(扫描速度：10mV/s，扫描范围：-1～0.5V)，于25℃下进行3个循环的扫描进行重构，将电化学重构前后的铜箔进行x-射线衍射测试，结果表明，经过电化学重构后的铜箔的(110)晶面的x-射线衍射峰明显增强，说明甲酸根诱导铜表面发生了重构；之后在-0.7V的恒电位电化学沉积30min，即可得到抗氧化处理的铜箔。Step 3: Electrochemical reconstruction and electrochemical deposition: At room temperature, using cyclic voltammetry (scanning speed: 10mV / s, scanning range: -1 to 0.5V), scan for 3 cycles at 25 ° C. Reconstruction. The copper foil before and after electrochemical reconstruction was subjected to x-ray diffraction test. The results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that the formate induced The copper surface was reconstituted; afterwards, it was deposited at a constant potential of -0.7V for 30 min to obtain an oxidation-resistant copper foil.
步骤四：乙醇清洗，干燥。Step 4: Wash with ethanol and dry.
将处理前后的铜箔在0.1M的NaOH溶液中室温放置10h之后分别进行SEM测试，结果表明经过甲酸盐修饰后的铜箔具有更光滑平整的表面，可见其抗氧化性得以了提高。The SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
实施例16：Embodiment 16:
步骤一：表面清洗：取25μm厚铜箔，裁成1×3cm 2长方形大小，浸泡在含1wt％甲酸的乙醇溶液中，并超声处理5min，洗去表面残留的有机物和氧化物，再用乙醇超声冲洗3次，氮气吹扫干燥。 Step 1: Surface cleaning: take 25μm thick copper foil, cut into 1 × 3cm 2 rectangles, soak it in an ethanol solution containing 1wt% formic acid, and sonicate for 5min, wash away the remaining organic matter and oxides on the surface, and then use ethanol Sonicate 3 times and dry with a nitrogen purge.
步骤二：电解液配制：干燥后的铜箔作为工作电极，饱和的甘汞电极为参比电极，铂片电极作为对电极。溶剂为水，同时加入1wt％的甲酸钠水溶液(pH＝10)作为电解质溶液。Step 2: electrolyte preparation: the dried copper foil is used as the working electrode, the saturated calomel electrode is used as the reference electrode, and the platinum sheet electrode is used as the counter electrode. The solvent was water, and at the same time, a 1 wt% aqueous sodium formate solution (pH = 10) was added as an electrolyte solution.
步骤三：电化学重构和电化学沉积：在室温下，采用方波伏安技术(扫描速度：10mV/s，扫描范围：-1～0.5V)，于35℃下进行5个循环的扫描进行重构，将电化学重构前后的铜箔进行x-射线衍射测试，结果表明，经过电化学重构后的铜箔的(110)晶面的x-射线衍射峰明显增强，说明甲酸根诱导铜表面发生了重构；之后在-0.6V的恒电位电化学沉积30min，即可得到抗氧化处理的铜箔。Step 3: Electrochemical reconstruction and electrochemical deposition: at room temperature, using square wave voltammetry (scanning speed: 10mV / s, scanning range: -1 ~ 0.5V), scanning at 35 ° C for 5 cycles After reconstruction, the copper foil before and after electrochemical reconstruction was subjected to x-ray diffraction test. The results showed that the x-ray diffraction peak of the (110) crystal plane of the copper foil after electrochemical reconstruction was significantly enhanced, indicating that formate Reconstruction of the copper surface was induced; then, a copper foil with anti-oxidation treatment was obtained by electrochemical deposition at a constant potential of -0.6V for 30 min.
步骤四：乙醇清洗，干燥。Step 4: Wash with ethanol and dry.
将处理前后的铜箔在0.1M的NaOH溶液中室温放置10h之后分别进行SEM测试，结果表明经过甲酸盐修饰后的铜箔具有更光滑平整的表面，可见其抗氧化性得以了提高。The SEM test was performed after the copper foil before and after treatment in a 0.1M NaOH solution at room temperature for 10 hours. The results showed that the copper foil modified with formate had a smoother and smoother surface, and its oxidation resistance was improved.
对比例1Comparative Example 1
按照实施例1的方法对铜箔进行表面处理，不同的是，不包括采用循环伏安技术进行电化学重构的步骤，而是直接将清洗后的铜箔在电解质溶液中进行恒电位电化学沉积，得到抗氧化处理的铜箔，将其进行SEM测试，结果表明，该铜箔在0.1M的NaOH溶液中室温放置10h之后，表面整体较为光滑平整，但局部有氧化腐蚀的情况出现，可见其抗氧化性提到了 一定程度的改善，但还仍有待提高。Surface treatment was performed on the copper foil according to the method of Example 1. The difference was that the step of electrochemical reconstruction using cyclic voltammetry was not included. Instead, the cleaned copper foil was subjected to potentiostatic electrochemistry in an electrolyte solution. After deposition, an anti-oxidation-treated copper foil was obtained, and the SEM test was performed. The results showed that the copper foil was left in a 0.1M NaOH solution at room temperature for 10 hours, and the entire surface was smooth and flat, but local oxidation corrosion appeared. Its oxidation resistance has been mentioned to a certain extent, but it still needs to be improved.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention. These simple modifications All belong to the protection scope of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合。为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。In addition, it should be noted that the specific technical features described in the foregoing specific embodiments can be combined in any suitable manner without conflict. In order to avoid unnecessary repetition, various possible combinations are not described separately in the present invention.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。In addition, various combinations of the embodiments of the present invention can also be arbitrarily combined, as long as it does not violate the idea of the present invention, it should also be regarded as the content disclosed by the present invention.

Claims (10)

  1. 一种铜材料抗氧化的电化学处理方法，其特征在于，该方法包括将铜材料作为工作电极，在含有稳定剂的电解质中依次进行电化学重构和电化学沉积，所述稳定剂为能够提供甲酸根的化合物，以使得所述铜材料的表面吸附有甲酸根。An anti-oxidation electrochemical treatment method for a copper material, characterized in that the method includes using the copper material as a working electrode, and sequentially performing electrochemical reconstruction and electrochemical deposition in an electrolyte containing a stabilizer, the stabilizer being capable of A formate compound is provided so that the formate is adsorbed on the surface of the copper material.
  2. 根据权利要求1所述的电化学处理方法，其特征在于，The method of electrochemical treatment according to claim 1, wherein:
    所述电解质为稳定剂和极性溶剂的混合溶液；The electrolyte is a mixed solution of a stabilizer and a polar solvent;
    优选地，所述稳定剂与极性溶剂的重量比为1︰10～1︰100。Preferably, the weight ratio of the stabilizer to the polar solvent is from 1:10 to 1: 100.
  3. 根据权利要求1所述的电化学处理方法，其特征在于，所述稳定剂为甲酸和/或甲酸盐。The method of claim 1, wherein the stabilizer is formic acid and / or formate.
  4. 根据权利要求3所述的电化学处理方法，其特征在于，所述甲酸盐选自甲酸锂、甲酸钠、甲酸铯、甲酸镁、三甲酸铝、甲酸钾、甲酸铵、甲酸钙、甲酸锌、甲酸铁、甲酸铜、甲酸锶、甲酸钡、甲酸铍、甲酸镍、甲酸钴和甲酸锰中的至少一种。The method according to claim 3, wherein the formate is selected from the group consisting of lithium formate, sodium formate, cesium formate, magnesium formate, aluminum triformate, potassium formate, ammonium formate, calcium formate, zinc formate, At least one of iron formate, copper formate, strontium formate, barium formate, beryllium formate, nickel formate, cobalt formate, and manganese formate.
  5. 根据权利要求1-4中任意一项所述的电化学处理方法，其特征在于，所述极性溶剂选自水、酰胺类溶剂、醇类溶剂、脂类溶剂和醚类溶剂中的至少一种；The method according to any one of claims 1 to 4, wherein the polar solvent is selected from at least one of water, amide solvents, alcohol solvents, lipid solvents, and ether solvents. Species
    所述酰胺类溶剂选自甲酰胺、二甲基甲酰胺、二乙基甲酰胺、二甲基乙酰胺、二乙基乙酰胺和二甲基丙酰胺中的至少一种；所述醇类溶剂选自一元醇、二元醇和多元醇中的至少一种；所述酯类溶剂选自乙酸乙酯、乙酸甲酯、乙酸正丁脂、乙酸正戊酯、戊酸乙酯、丙酸乙酯、丁酸乙酯、乳酸乙酯、壬酸乙酯、磷酸三乙酯、己酸乙酯、甲酸乙酯、环己甲酸乙酯、庚酸乙酯和肉桂酸乙酯中的至少一种；所述醚类溶剂选自甲醚、***、二苯醚、环氧乙烷和四氢呋喃中的至少一种。The amide solvent is selected from at least one of formamide, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, and dimethylpropanamide; the alcohol solvent At least one selected from the group consisting of a monohydric alcohol, a dihydric alcohol, and a polyhydric alcohol; the ester solvent is selected from the group consisting of ethyl acetate, methyl acetate, n-butyl acetate, n-pentyl acetate, ethyl valerate, and ethyl propionate At least one of ethyl butyrate, ethyl lactate, ethyl nonanoate, triethyl phosphate, ethyl hexanoate, ethyl formate, ethyl cyclohexanoate, ethyl heptanoate and ethyl cinnamate; The ether-based solvent is selected from at least one of methyl ether, diethyl ether, diphenyl ether, ethylene oxide, and tetrahydrofuran.
  6. 根据权利要求1-4中任意一项所述的电化学处理方法，其特征在于，所述电解质的pH范围为4～13，优选为5～11。The method according to any one of claims 1 to 4, wherein the pH of the electrolyte ranges from 4 to 13, and preferably from 5 to 11.
  7. 根据权利要求1-4中任意一项所述的电化学处理方法，其特征在于，所述电化学重构 采用循环伏安技术、方波伏安技术和差分脉冲伏安技术中的至少一种进行；所述电化学沉积采用恒电位沉积法、恒电流沉积法和欠电位沉积法中的至少一种进行。The electrochemical processing method according to any one of claims 1 to 4, wherein the electrochemical reconstruction uses at least one of a cyclic voltammetry technique, a square wave voltammetry technique, and a differential pulse voltammetry technique. The electrochemical deposition is performed by at least one of a potentiostatic deposition method, a constant current deposition method, and an underpotential deposition method.
  8. 根据权利要求7所述的电化学处理方法，其特征在于，所述电化学重构的电化学窗口为-5V～5V，扫描速度为10 -1～10 3mV/s。 The method of claim 7, wherein the electrochemical window for electrochemical reconstruction is -5V to 5V, and the scanning speed is 10 -1 to 10 3 mV / s.
  9. 根据权利要求7所述的电化学处理方法，其特征在于，所述恒电位沉积法的电位范围为-5V～5V，所述恒电流沉积法的电流范围为10 -3～10 3mA/cm 2。 The method of claim 7, wherein the potential range of the potentiostatic deposition method is -5V to 5V, and the current range of the constant current deposition method is 10 -3 to 10 3 mA / cm 2 .
  10. 根据权利要求7所述的电化学处理方法，其特征在于，所述电化学重构的温度为-70～200℃，当所述电化学重构采用循环伏安技术时，扫描圈数为1～1000圈；所述电化学沉积的温度为-70～200℃，时间为0.1～1000min。The electrochemical processing method according to claim 7, wherein the electrochemical reconstruction temperature is -70 to 200 ° C, and when the electrochemical reconstruction uses a cyclic voltammetry technique, the number of scanning cycles is 1 ～ 1000 turns; the temperature of the electrochemical deposition is -70-200 ° C, and the time is 0.1-1000min.
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