Electrochemical device capable of observing deposition process of electrolytic copper foil in situ

Abstract

The invention provides an electrochemical device capable of observing the deposition process of an electrolytic copper foil in situ, the electrochemical device comprises a metal bottom sheet and a transparent plastic ring arranged on the metal bottom sheet, the metal bottom sheet and the transparent plastic ring are enclosed to form an electrolytic tank, the transparent plastic ring is provided with a metal cathode strip and a plurality of anode strips, and the anode strips are arranged on the metal bottom sheet. The cathode strip and the anode strip penetrate through the transparent plastic ring in parallel, the anode strip is located above the cathode strip, a heat source is arranged at the bottom of the metal bottom sheet to heat the metal bottom sheet at a constant temperature to keep the working temperature of the electrolyte, and the cathode strip and the anode strip are used for being connected with a negative electrode and a positive electrode of a power source respectively. And the power supply is connected with the constant potential rectifier to control the electrodeposition current of the copper. According to the method, the growth process of copper grains can be observed in situ when copper is electrodeposited on the surface of titanium metal, and the formation and growth process of the copper grains is changed under the action of different deposition currents and additives.

Description

Technical Field

[0001] The invention relates to the technical field of copper foil production technology, and in particular to an electrochemical device capable of in-situ observing the deposition process of electrolytic copper foil. Background Art

[0002] Electrolytic copper foil is a process in which copper ions in a copper sulfate solution are reduced and copper is precipitated on a negatively charged metal cylinder by an electrochemical method. The copper foil formed is electrolytic copper foil.

[0003] The electroplating process of copper foil on metal mainly includes the adsorption, reduction, grain formation and growth of copper ions. Different electrolysis conditions, including the applied current, electrolysis temperature, additive type and other control parameters, will directly affect the deposition process of copper on metal, and ultimately lead to the formation of different crystalline structures of copper foil. At present, the influence of these control parameters on the performance of copper foil products is mainly judged by testing the physical and chemical properties of copper foil products, and there is a lack of relevant information on the grain formation and growth process in the early stage of copper foil formation. These relevant information can provide a basis for theoretical research on the formation process of electrolytic copper foil and provide a reference for the development of new copper foil products.

[0004] In the existing electrochemical device for in-situ observation of the electrolytic copper foil deposition process, a copper plate and a zinc plate are usually connected by a wire, and fixed in a beaker containing a sulfuric acid solution by a duckbill clamp for reaction. During the in-situ observation, a high-power microscope is used to focus to observe the deposition process of the electrolytic copper foil. However, during the copper deposition process of the device, the duckbill clamp will block the reaction area, resulting in inaccurate focusing of the high-power microscope, and even unable to observe a clear image, thereby affecting the effect of the in-situ observation. Summary of the invention

[0005] Based on this, an object of the present invention is to provide an electrochemical device capable of in-situ observation of the electrolytic copper foil deposition process, so as to at least solve the deficiencies in the above-mentioned technology.

[0006] The present invention provides an electrochemical device capable of in-situ observing the deposition process of electrolytic copper foil, comprising a metal bottom sheet and a transparent plastic ring arranged on the metal bottom sheet, wherein the metal bottom sheet and the transparent plastic ring are combined to form an electrolytic cell, a metal cathode strip and a plurality of anode strips are arranged on the transparent plastic ring, the cathode strip and the anode strip both penetrate the transparent plastic ring in parallel, and the anode strip is located above the cathode strip, the anode strip and the connection between the cathode strip and the transparent plastic ring are sealed, a heat source is arranged at the bottom of the metal bottom sheet to heat the metal bottom sheet at a constant temperature to maintain the working temperature of the electrolyte, the cathode strip and the anode strip are respectively used to connect the negative electrode and the positive electrode of a power supply, and the power supply controls the copper electrodeposition current by connecting to a constant potentiostat.

[0007] Furthermore, the height of the transparent plastic ring is less than 15 mm and the diameter is less than 20 mm. Small holes for fixing the anode strip and the cathode strip are symmetrically opened on both sides of the transparent plastic ring, and the distance between any two of the small holes is 3 mm to 5 mm.

[0008] Furthermore, there are two anode bars, which are distributed vertically and parallel to the cathode bar, wherein the two anode bars are respectively located at the upper left and upper right of the cathode bar, the height difference between the anode bar and the cathode bar ranges from 3mm to 5mm, and the distance between the two anode bars is 3mm to 5mm.

[0009] Furthermore, the transparent plastic ring is sealed and bonded to the metal bottom sheet by glue, so that the metal bottom sheet serves as the base of the electrolytic cell.

[0010] Furthermore, the metal bottom plate includes a stainless steel bottom plate, the cathode strip includes a metal titanium strip, and the anode strip includes a platinum wire or a titanium wire with a surface modified with iridium dioxide.

[0011] Furthermore, the diameter of the anode strip is less than 3 mm, and both sides or one side of the cathode strip are sealed and insulated with epoxy resin glue.

[0012] Furthermore, the heat source is a constant temperature heating device, and the heating constant temperature of the constant temperature heating device is 50°C~70°C.

[0013] Furthermore, the thickness of the metal bottom sheet is less than 2 mm.

[0014] Furthermore, the transparent plastic ring is made of one or more of polyacrylic acid, polycarbonate, and polyethylene.

[0015] The electrochemical device of the present invention can observe the deposition process of electrolytic copper foil in situ. By setting a transparent plastic ring on the metal bottom plate, the observation of the deposition process of electrolytic copper foil can be more intuitive. By fixing the cathode strip and the anode strip and setting a heat source at the bottom of the metal bottom plate, the metal bottom plate can be heated at a constant temperature to maintain the working temperature of the electrolyte. The copper electrodeposition current is controlled by a constant potentiostat. An optical electron microscope is used to observe in situ the growth process of copper grains when copper is electrodeposited on the metal surface. Under the action of different deposition currents and additives, the formation and growth process of copper grains changes. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 A three-dimensional diagram of an electrochemical device capable of in-situ observation of an electrolytic copper foil deposition process in a first embodiment of the present invention; Figure 2 A three-dimensional diagram of a transparent plastic ring of an electrochemical device capable of in-situ observation of an electrolytic copper foil deposition process in a first embodiment of the present invention; Figure 3 A top view of an electrochemical device capable of in-situ observation of an electrolytic copper foil deposition process in a first embodiment of the present invention; Figure 4 This is an experimental diagram of copper deposition on an electrode rod of an electrochemical device capable of in-situ observation of the electrolytic copper foil deposition process in the first embodiment of the present invention.

[0017] Description of main component symbols:

[0018] The following specific implementation manner will further illustrate the present invention in conjunction with the above-mentioned drawings. DETAILED DESCRIPTION

[0019] In order to facilitate the understanding of the present invention, the present invention will be described more fully below with reference to the relevant drawings. Several embodiments of the present invention are given in the drawings. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thorough and comprehensive.

[0020] It should be noted that when an element is referred to as being "fixed to" another element, it may be directly on the other element or there may be a central element. When an element is considered to be "connected to" another element, it may be directly connected to the other element or there may be a central element at the same time. The terms "vertical", "horizontal", "left", "right" and similar expressions used herein are for illustrative purposes only.

[0021] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0022] Embodiment 1 See also Figures 1 to 3, shown is an electrochemical device capable of in-situ observation of the deposition process of electrolytic copper foil in the first embodiment of the present invention, comprising a metal bottom sheet 2 and a transparent plastic ring 1 fixed on the metal bottom sheet 2, wherein the transparent plastic ring 1 is sealed and bonded to the metal bottom sheet 2 by glue, so that the metal bottom sheet 2 serves as the base of the electrolytic cell, a metal cathode strip 3 and a plurality of anode strips 4 are arranged on the transparent plastic ring 1, the cathode strip 3 and the anode strip 4 both penetrate the transparent plastic ring 1 in parallel, and the anode strip 4 is located above the cathode strip 3, the anode strip and the connection between the cathode strip and the transparent plastic ring are sealed, a heat source is arranged at the bottom of the metal bottom sheet 2 to heat the metal bottom sheet 2 at a constant temperature to maintain the working temperature of the electrolyte, a constant potentiostat is used to control the electrodeposition current of copper, and an optical electron microscope is used to directly observe the deposition process of the cathode strip 3.

[0023] It is understandable that the plastic ring is made of transparent material, so that the observation of the electrolytic copper foil deposition process can be more intuitive, and the growth process of copper grains when copper is electro-deposited on the metal surface can be observed in situ. Under the action of different deposition currents and additives, the formation and growth process of copper grains changes. In this embodiment, the height of the transparent plastic ring 1 is less than 15mm and the diameter is less than 20mm, and its material is one or more of polyacrylic acid, polycarbonate, and polyethylene. Preferably, the material of the transparent plastic ring 1 is made of polyacrylic acid.

[0024] In this embodiment, small holes for fixing the anode strip 4 and the cathode strip 3 are symmetrically opened on both sides of the transparent plastic ring 1. The distance between the two small holes for fixing the anode strip 4 is 3mm~5mm, and the distance between the small hole for fixing the cathode strip 3 and the other two small holes is 3mm~5mm.

[0025] Specifically, there are two anode bars 4, which are distributed vertically and parallelly between the two anode bars 4 and the cathode bar 3, wherein the two anode bars 4 are respectively located at the upper left and upper right of the cathode bar 3, the height difference between the anode bar 4 and the cathode bar 3 ranges from 3 mm to 5 mm, and the distance between the two anode bars 4 is 3 mm to 5 mm. In the present embodiment, the anode bar 4 includes a platinum wire or a titanium wire with a surface modified with iridium dioxide.

[0026] Preferably, the metal bottom plate 2 is made of stainless steel with a thickness less than 2 mm; the cathode strip 3 is made of metal titanium strip, and the anode strip 4 is made of platinum wire.

[0027] It should be noted that the microscope used in this embodiment is a high-power microscope (1000 times), see Figure 4, shown is an experimental diagram of copper deposition on the electrode rods of the device in this embodiment, wherein the left area is the electrode package area where copper is not deposited, and the right area is the exposed electrode area where copper is deposited. It can be seen that (1) the distance between the anode rods is less than 3 mm, which is not conducive to the focusing operation of the microscope on the electrode surface; when the distance between the anode rods is greater than 5 mm, it can be observed that the copper deposition process at both ends of the electrode is significantly faster than that in the middle. (2) When the distance between the anode and the cathode is less than 3 mm, it can be observed that the copper deposition process at both ends of the electrode is significantly faster than that in the middle; when it is greater than 5 mm, the cathode is far away from the liquid surface. Since the electrolyte is a blue copper sulfate solution, the optical microscope is not clearly focused, affecting the observation effect.

[0028] Secondly, the distance between the electrode rods is controlled at 3mm~5mm, which can make the current density more uniform and better facilitate the deposition effect of the cathode strip 3; the position of the anode strip is higher than that of the cathode strip, which can better facilitate the high-power microscope to directly observe the in-situ deposition process from the side of the transparent plastic ring, which is more intuitive than the vertical method in the prior art.

[0029] In this embodiment, the cathode strip 3 is configured as a long strip, which can help fix the electrode on the one hand, and on the other hand, the planar structure of the electrode helps focus the optical microscope and observe the surface state of the electrode.

[0030] Furthermore, the diameter of the anode strip 4 is less than 3 mm, and both sides or one side of the cathode strip 3 are sealed and insulated with epoxy resin glue.

[0031] Furthermore, the heat source is a constant temperature heating device, and the heating constant temperature of the constant temperature heating device is 50°C~70°C.

[0032] It should be noted that a heating plate is placed under the stainless steel sheet, the stainless steel sheet is fixed on the sample stage using the metal clip on the optical microscope sample stage, the prepared electrolyte is added to the plastic ring, the titanium bar is connected to the negative pole of the power supply, the anode wire is connected to the positive pole of the power supply, the electrolyte temperature is raised to between 50 and 55°C through the heating plate, the electrodeposition current parameters are adjusted, the optical microscope is focused on the surface of the titanium bar, the magnification is set, the power switch is turned on to start copper electrodeposition, and the initial process of copper electrodeposition on the surface of the titanium bar is directly observed through a microscope.

[0033] In this embodiment, the electrolyte Cu 2+ The concentration is 90g / L, the concentration of H2SO4 is 100g / L, and the concentration of Cl - The concentration is 10ppm. The prepared electrolyte is added to the plastic ring. The titanium strip is connected to the negative pole of the power supply, and the anode wire is connected to the positive pole of the power supply. The electrolyte temperature is raised to between 50 and 55°C through the heating plate. The deposition current density is 10A / dm 2, focus the optical microscope on the surface of the titanium strip, adjust the magnification to 1000 times, turn on the power switch to start copper electrodeposition, and directly observe the initial process of copper electrodeposition on the surface of the titanium strip through the microscope.

[0034] In some optional embodiments, the prepared electrolyte Cu 2+ The concentration is 90g / L, the concentration of H2SO4 is 100g / L, and the concentration of Cl - The concentration is 10ppm, the gelatin concentration is 100ppm, the prepared electrolyte is added to the plastic ring, the titanium strip is connected to the negative pole of the power supply, the anode wire is connected to the positive pole of the power supply, and the electrolyte temperature is raised to between 50 and 55°C through the heating plate. The deposition current density is 10A / dm 2 , focus the optical microscope on the surface of the titanium strip, adjust the magnification to 1000 times, turn on the power switch to start copper electrodeposition, and directly observe the initial process of copper electrodeposition on the surface of the titanium strip through the microscope.

[0035] In some optional embodiments, the prepared electrolyte Cu 2+ The concentration is 90g / L, the concentration of H2SO4 is 100g / L, and the concentration of Cl - The concentration is 10ppm, the SPS concentration is 50ppm, the prepared electrolyte is added to the plastic ring, the titanium strip is connected to the negative pole of the power supply, the anode wire is connected to the positive pole of the power supply, and the electrolyte temperature is raised to between 50 and 55°C through the heating plate. The deposition current density is 10A / dm 2 , focus the optical microscope on the surface of the titanium strip, adjust the magnification to 1000 times, turn on the power switch to start copper electrodeposition, and directly observe the initial process of copper electrodeposition on the surface of the titanium strip through the microscope.

[0036] In some optional embodiments, the prepared electrolyte Cu 2+ The concentration is 90g / L, the concentration of H2SO4 is 100g / L, and the concentration of Cl - The concentration is 10ppm. The prepared electrolyte is added to the plastic ring. The titanium strip is connected to the negative pole of the power supply, and the anode wire is connected to the positive pole of the power supply. The electrolyte temperature is raised to between 50 and 55°C through the heating plate. The deposition current density is 20A / dm 2 , focus the optical microscope on the surface of the titanium strip, adjust the magnification to 1000 times, turn on the power switch to start copper electrodeposition, and directly observe the initial process of copper electrodeposition on the surface of the titanium strip through the microscope.

[0037] It has been verified that the electrochemical device in this embodiment can be used to in-situ observe the growth process of copper grains when copper is electrodeposited on the titanium metal surface. Under the action of different deposition currents and additives, the formation and growth process of copper grains changes.

[0038] In summary, the electrochemical device capable of in-situ observation of the electrolytic copper foil deposition process in the above-mentioned embodiments of the present invention, by providing a transparent plastic ring on the metal substrate, makes the observation of the electrolytic copper foil deposition process more intuitive, by fixing the cathode strips and the anode strips and providing a heat source at the bottom of the metal substrate, the metal substrate can be heated at a constant temperature to maintain the working temperature of the electrolyte, and a constant potentiostat is used to control the copper electrodeposition current, and an optical electron microscope is used to in-situ observe the growth process of copper grains when copper is electrodeposited on the metal surface, and the formation and growth process of copper grains changes under the action of different deposition currents and additives.

Claims

1. An electrochemical device capable of in-situ observation of the electrolytic copper foil deposition process, characterized in that: The invention comprises a metal bottom sheet and a transparent plastic ring arranged on the metal bottom sheet, wherein the metal bottom sheet and the transparent plastic ring are combined to form an electrolytic cell, a metal cathode strip and a plurality of anode strips are arranged on the transparent plastic ring, the cathode strip and the anode strip both penetrate the transparent plastic ring in parallel, and the anode strip is located above the cathode strip, the anode strip and the connection between the cathode strip and the transparent plastic ring are sealed, a heat source is arranged at the bottom of the metal bottom sheet to heat the metal bottom sheet at a constant temperature to maintain the working temperature of the electrolyte, the cathode strip and the anode strip are respectively used to connect the negative pole and the positive pole of a power supply, and the power supply controls the copper electrodeposition current by connecting to a constant potentiostat.

2. The electrochemical device capable of in-situ observation of electrolytic copper foil deposition process according to claim 1, characterized in that: The height of the transparent plastic ring is less than 15 mm and the diameter is less than 20 mm. Small holes for fixing the anode strip and the cathode strip are symmetrically opened on both sides of the transparent plastic ring, and the distance between any two of the small holes is 3 mm to 5 mm.

3. The electrochemical device capable of in-situ observation of electrolytic copper foil deposition process according to claim 1, characterized in that: There are two anode bars, which are distributed vertically and parallel to the cathode bar, wherein the two anode bars are respectively located at the upper left and upper right of the cathode bar, the height difference between the anode bar and the cathode bar ranges from 3mm to 5mm, and the distance between the two anode bars is 3mm to 5mm.

4. The electrochemical device capable of in-situ observation of electrolytic copper foil deposition process according to claim 1, characterized in that: The transparent plastic ring is sealed and bonded to the metal bottom sheet by glue, so that the metal bottom sheet serves as the base of the electrolytic cell.

5. The electrochemical device capable of in-situ observation of electrolytic copper foil deposition process according to claim 1, characterized in that: The metal bottom plate comprises a stainless steel bottom plate, the cathode strip comprises a metal titanium strip, and the anode strip comprises a platinum wire or a titanium wire with the surface modified with iridium dioxide.

6. The electrochemical device capable of in-situ observation of electrolytic copper foil deposition process according to claim 1, characterized in that: The diameter of the anode strip is less than 3 mm, and both sides or one side of the cathode strip are sealed and insulated with epoxy resin glue.

7. The electrochemical device capable of in-situ observation of electrolytic copper foil deposition process according to claim 1, characterized in that: The heat source is a constant temperature heating device, and the heating constant temperature of the constant temperature heating device is 50°C~70°C.

8. The electrochemical device capable of in-situ observation of electrolytic copper foil deposition process according to claim 1, characterized in that: The thickness of the metal bottom sheet is less than 2 mm, the height of the transparent plastic ring is less than 15 mm, and the diameter is less than 20 mm.

9. The electrochemical device capable of in-situ observation of electrolytic copper foil deposition process according to claim 1, characterized in that: The transparent plastic ring is made of one or more of polyacrylic acid, polycarbonate and polyethylene.

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