Preparation method of high-entropy alloy electrode for tunneling oxide passivation contact cell

Abstract

The invention belongs to the technical field of electronic materials, and particularly relates to a preparation method of a high-entropy alloy electrode for a tunneling oxide layer passivation contact battery. The preparation method comprises the steps of tunneling oxide layer passivation contact cell cleaning, laser grooving, acid oxidation liquid reverse electroplating, alkaline oxidation liquid reverse electroplating, leaching, high-entropy alloy electrode electroplating and vacuum annealing. The high-entropy alloy electrode is good in conductivity and strong in binding force with a tunneling oxide layer passivation contact cell, and can pass an ammonia corrosion test, and 100% of the electrode coating does not fall off. The preparation of the high-entropy alloy electrode only needs one-time electroplating, the process route is short, the cost is low, and the high-entropy alloy electrode is suitable for large-scale popularization and application.

Description

Preparation method of high-entropy alloy electrode for tunnel oxide passivated contact battery Technical Field

[0001] This invention belongs to the field of electronic materials, specifically relating to a method for preparing a high-entropy alloy electrode for a tunnel oxide passivated contact battery. Background Technology

[0002] Tunneling oxide passivated contact solar cells (TOPCon cells) are a high-efficiency solar cell technology that has become the mainstream choice in the current photovoltaic market, with mass production efficiencies exceeding 25% and a theoretical limit of 28.7%. TOPCon cells form a passivated contact structure by constructing an ultra-thin silicon dioxide tunneling layer and a doped polycrystalline silicon layer on the back of an N-type silicon wafer. The tunneling oxide layer allows electrons to tunnel through while blocking hole recombination, reducing carrier loss. The polycrystalline silicon layer collects current and enables selective transport, increasing the open-circuit voltage. The N-type silicon substrate exhibits almost no light-induced degradation, with only 1% degradation in the first year, far lower than the 2% of PERC. It has a low temperature coefficient of -0.26% / ℃, resulting in less power loss at high temperatures. With a bifaciality >85%, its low-light power generation capability is 5% higher than PERC, making it suitable for cloudy days or low-irradiance scenarios in the early morning or late evening.

[0003] The copper plating process for TOPCon batteries is an advanced metallization technology designed to reduce silver paste usage and achieve "silver-free" plating. It deposits copper grid lines on the battery surface using electrochemical methods to replace or reduce the use of traditional silver paste. The process mainly consists of: Seed layer deposition: A very thin metal seed layer (such as a copper or nickel-copper composite layer) is deposited on the polycrystalline silicon contact area of ​​the TOPCon battery (usually formed by laser-windowed LCO). This provides a conductive path and enhances the adhesion of subsequent copper plating; this step is a prerequisite for electroplating. Patterning (mask): A photosensitive material (photoresist) is coated on the battery surface, and a precise grid line pattern is formed using photolithography. The areas not exposed to light (i.e., the parts where grid lines need to be formed) are retained after development as a mask for electroplating, while other areas are removed. Electroplating deposition: The battery is immersed in an electrolyte containing copper ions (such as copper sulfate). When current is applied, copper ions are reduced and deposited in the areas exposed by the seed layer (i.e., the grid line pattern), forming thick copper wires. This process enables extremely fine linewidths (e.g., <25μm) and significantly reduces resistance. Post-processing: After electroplating, the remaining photoresist mask and part of the seed layer need to be removed to finally form a complete copper metallized structure. The advantage of this process is that it can effectively reduce the metallization cost of the battery (copper is much cheaper than silver), while improving the contact resistance helps to improve the battery's open-circuit voltage (Voc) and overall conversion efficiency.

[0004] Copper plating has significant cost advantages, but its disadvantages are equally significant: (1) Copper cannot directly contact the silicon wafer of the TOPCon cell, otherwise it will diffuse within the silicon wafer, damaging the photoelectric conversion efficiency of the solar cell; (2) Copper itself is not corrosion resistant and needs to be plated with a layer of tin or silver for protection. Even so, the long-term reliability of the copper electrode cannot be guaranteed. High-entropy alloys are alloys formed by five or more metals in equal or approximately equal amounts. They have excellent fracture resistance, tensile strength, corrosion resistance, and oxidation resistance. If high-entropy alloys can replace copper electrodes, it is expected to reduce process steps and improve electrode reliability.

[0005] High-entropy alloys are mostly prepared by smelting, which involves extremely high processing temperatures and is incompatible with the TOPCon battery manufacturing process. If a wet electroplating process can be used to create grooves on TOPCon batteries and electroplat high-entropy alloy electrodes, it is hoped that the above problems can be solved. Summary of the Invention

[0006] The purpose of this invention is to propose a method for preparing a high-entropy alloy electrode for tunnel oxide passivation contact batteries, replacing the multi-step metal deposition method in the traditional process with a one-step high-entropy alloy deposition method.

[0007] The method for preparing a high-entropy alloy electrode for a tunnel oxide passivation contact battery proposed in this invention comprises the following steps: (1) Cleaning the battery: The tunnel oxide passivation contact battery is rinsed sequentially with deionized water, ethanol, and acetone, and then placed in a vacuum oven and dried at 50~60℃ to obtain a clean tunnel oxide passivation contact battery; (2) Laser grooving: The clean tunnel oxide passivation contact battery is placed under a laser and scanned for 3~5 seconds with an ultraviolet laser with a power of 5W and a wavelength of 320~400nm to obtain a grooved battery; (3) Reverse electroplating with acidic oxide solution: The grooved battery is placed in an acidic oxide solution, with the grooved battery as the anode and the titanium mesh electrode as the cathode, and the current density is controlled to be 1~2A / dm 2 Electroplating for 2-3 minutes, then removing, rinsing with deionized water, and drying with nitrogen to obtain an acid-treated battery; wherein, the weight ratio of each component in the acidic oxidation solution is hydrochloric acid: hydrogen peroxide: sodium chloride: deionized water = 1: (1-1.5): (0.1-0.2): (20-25); (4) Alkaline oxidation solution reverse electroplating: place the acid-treated battery in the alkaline oxidation solution, with the acid-treated battery as the anode and the titanium mesh electrode as the cathode, and control the current density to be 0.5-1A / dm 2Electroplating for 3-5 minutes, then removing, rinsing with deionized water, and drying with nitrogen to obtain an alkaline-treated battery; wherein, the weight ratio of each component in the alkaline oxidation solution is ammonia: hydrogen peroxide: sodium hydroxide: deionized water = 1: (1-1.3): (0.2-0.3): (25-30); (5) Preparation of high-entropy alloy electrode: The alkaline-treated battery is placed in a high-entropy alloy electroplating solution, with the alkaline-treated battery as the cathode and the platinum electrode as the anode, and the current density is controlled at 2-3 A / dm 2 Electroplating for 5-10 minutes, then removing, rinsing with deionized water, drying with nitrogen, and then placing in a vacuum oven for annealing at 300-350℃ for 3-5 hours, followed by cooling, yields a high-entropy alloy electrode for use in tunnel oxide layer passivation contact batteries. The components and concentrations in the high-entropy alloy electroplating solution are as follows: cobalt sulfate 20-30 g / L, nickel sulfate 20-30 g / L, chromium trichloride 20-30 g / L, stannous chloride 20-30 g / L, zinc sulfate 20-30 g / L, trisodium citrate 100-150 g / L, glycine 40-60 g / L, ammonium sulfate 100-150 g / L, naphthol sulfonic acid 1-2 g / L, with the pH adjusted to 2-3 using a 1M dilute sulfuric acid aqueous solution, and the remainder being deionized water.

[0008] The corrosion resistance of high-entropy alloy electrodes was tested in accordance with the standard GB / T 43058-2023 "Ammonia Corrosion Test of Photovoltaic Modules".

[0009] The bonding strength between the high-entropy alloy electrode and the tunneling oxide passivated contact cell was tested in accordance with the standard ASTM D 3359, "Standard Test Methods for Rating Adhesion by Tape Test".

[0010] The resistivity of the high-entropy alloy electrode was tested in accordance with the standard ASTM B193, "Standard Test Method for Resistivity of Electrical Conductor Materials".

[0011] The present invention has the following advantages: reverse electroplating with acidic oxidation solution combined with reverse electroplating with alkaline oxidation solution exposes the conductive silicon wafer after laser grooving, improves conductivity, and helps to improve the uniformity, integrity and conductivity of subsequent electroplating electrodes.

[0012] Replacing traditional Ni / Cu / Sn electrodes with high-entropy alloys reduces the number of metal electrode deposition steps, which can significantly reduce process costs.

[0013] Unlike ordinary alloys, high-entropy alloys exhibit a cocktail effect, making them more corrosion-resistant and thus improving the long-term reliability and lifespan of tunnel oxide passivated contact batteries.

[0014] Hongyuan New Materials (Xuzhou) Co., Ltd. disclosed a TOPCon solar cell electrode electroplating process (CN121001437A), including the following steps: S1: Laser grooving is performed on the front and back layers of an N-type silicon wafer to create front and back grid patterns, exposing the p+ emitter and n+ field region; S2: The grouted area of ​​the n+ field region is pre-cleaned; S3: The N-type silicon wafer is placed in electroplating device one for electroplating; S4: The grouted area of ​​the p+ emitter is pre-cleaned; S5: The N-type silicon wafer is placed in electroplating device two for electroplating; S6: The N-type silicon wafer is subjected to high-temperature annealing. Utilizing copper and nickel electroplating technology can reduce or eliminate the use of silver paste, thereby reducing non-silicon costs in the battery manufacturing process and alleviating and improving the problem of runaway silver prices caused by the increasing use of silver in photovoltaic solar cells. This invention uses copper and nickel electroplating technology to prepare multilayer electrodes, which is a traditional process. This invention prepares a high-entropy alloy single-layer electrode; the processes, electrode compositions, and structures are different.

[0015] East China University of Science and Technology has disclosed a bifacial TOPCon cell structure (CN118136700A) using electrochemical deposition to fabricate electrodes. The structure includes an N-type silicon substrate in the center, with tunneling oxide layers on both sides. A boron-doped polycrystalline silicon layer is deposited above the tunneling oxide layer on the front side, and a phosphorus-doped polycrystalline silicon layer is deposited below the tunneling oxide layer on the back side. Silicon nitride antireflective layers are deposited on the exterior of both the boron-doped and phosphorus-doped polycrystalline silicon layers. Electrodes are disposed on the silicon nitride antireflective layer. The cell is fabricated using N-type crystalline silicon as the substrate through a series of processes. Laser etching is performed on both sides of the S6-treated N-type silicon substrate to create trenches for electrochemical deposition in the electrode area. Electroless nickel plating is then performed at the trenches, followed by electrochemical deposition of nickel, copper, and tin to obtain the bifacial TOPCon cell. The invention requires a chemical nickel plating base and involves four steps of electrode metal deposition. The present invention uses acidic oxidation solution reverse electroplating combined with alkaline oxidation solution reverse electroplating to utilize the conductivity of the silicon wafer itself to electroplat a high-entropy electrode. The two processes have different routes, electrode components, and structures. Attached Figure Description

[0016] Figure 1 is an electron microscope image of the high-entropy alloy electrode for tunneling oxide passivation contact battery prepared in Example 1. Figure 2 is an optical image of the high-entropy alloy electrode for tunneling oxide passivation contact battery prepared in Example 1. Figure 3 is an optical image of the high-entropy alloy electrode for tunneling oxide passivation contact battery prepared in Example 1 before (a) and after (b) the tape peeling test. Detailed Implementation

[0017] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. Embodiment 1

[0018] (1) Cleaning the battery: The tunneling oxide passivated contact battery is rinsed with deionized water, ethanol and acetone in sequence, and then placed in a vacuum oven and dried at 50°C to obtain a clean tunneling oxide passivated contact battery; (2) Laser grooving: The clean tunneling oxide passivated contact battery is placed under a laser and scanned for 3 seconds with an ultraviolet laser with a power of 5W and a wavelength of 320~400nm to obtain a grooved battery; (3) Reverse electroplating with acidic oxide solution: The grooved battery is placed in an acidic oxide solution, with the grooved battery as the anode and the titanium mesh electrode as the cathode, and the current density is controlled at 1A / dm 2 Electroplating for 2 minutes, then removing, rinsing with deionized water, and drying with nitrogen to obtain an acid-treated battery; wherein, the weight ratio of each component in the acidic oxidation solution is hydrochloric acid: hydrogen peroxide: sodium chloride: deionized water = 1:1:0.1:20; (4) Alkaline oxidation solution reverse electroplating: the acid-treated battery is placed in the alkaline oxidation solution, with the acid-treated battery as the anode and the titanium mesh electrode as the cathode, and the current density is controlled at 0.5A / dm 2 Electroplating for 3 minutes, then removing, rinsing with deionized water, and drying with nitrogen to obtain an alkaline-treated battery; wherein, the weight ratio of each component in the alkaline oxidation solution is ammonia: hydrogen peroxide: sodium hydroxide: deionized water = 1:1:0.2:25; (5) Preparation of high-entropy alloy electrode: The alkaline-treated battery is placed in a high-entropy alloy electroplating solution, with the alkaline-treated battery as the cathode and the platinum electrode as the anode, and the current density is controlled at 2A / dm 2 Electroplating for 10 minutes, then removing, rinsing with deionized water, drying with nitrogen, and then placing in a vacuum oven for annealing at 350℃ for 3 hours, followed by cooling, yields a high-entropy alloy electrode for use in tunnel oxide layer passivation contact batteries. The components and concentrations in the high-entropy alloy electroplating solution are as follows: cobalt sulfate 20g / L, nickel sulfate 20g / L, chromium trichloride 20g / L, stannous chloride 20g / L, zinc sulfate 20g / L, trisodium citrate 100g / L, glycine 40g / L, ammonium sulfate 100g / L, naphthol sulfonic acid 1g / L, pH adjusted to 2-3 with 1M dilute sulfuric acid aqueous solution, with the remainder being deionized water.

[0019] The corrosion resistance of the high-entropy alloy electrode was tested in accordance with the standard GB / T 43058 2023 "Ammonia Corrosion Test for Photovoltaic Modules", and the adhesion between the high-entropy alloy electrode and the tunnel oxide passivated contact cell was tested in accordance with the standard ASTM D 3359 "Standard Test Methods for Rating Adhesion by Tape Test".

[0020] Referring to the standard ASTM B193, "Standard Test Method for Resistivity of Electrical Conductor Materials", the resistivity of the high-entropy alloy electrode was tested to be 2.44 μΩ·cm, which is higher than that of copper (1.68 μΩ·cm) and lower than that of nickel (6.84 μΩ·cm).

[0021] Figure 1 is an electron microscope image of the high-entropy alloy electrode used for tunnel oxide passivation contact battery prepared in Example 1. As can be seen from Figure 1, the metal on the surface of the high-entropy alloy is relatively densely packed.

[0022] Figure 2 is an optical photograph of the high-entropy alloy electrode for tunnel oxide passivation contact battery prepared in Example 1. As can be seen from Figure 2, the high-entropy alloy is relatively uniformly distributed in the tank, and there are no broken wires or over-plating phenomena on the electrode.

[0023] Figure 3 shows optical photographs of the high-entropy alloy electrode prepared in Example 1 for tunneling oxide layer passivated contact cells before (a) and after (b) the ammonia corrosion test and tape peeling test. As can be seen from Figure 3, the surface morphology of the high-entropy alloy electrode remained unchanged after the ammonia corrosion test, and it passed the tape adhesion test with a grade of 5B (100% no peeling), indicating that the high-entropy alloy electrode prepared by this invention has good reliability. Example 2

[0024] (1) Cleaning the battery: The tunneling oxide passivated contact battery is rinsed with deionized water, ethanol and acetone in sequence, and then placed in a vacuum oven and dried at 60°C to obtain a clean tunneling oxide passivated contact battery; (2) Laser grooving: The clean tunneling oxide passivated contact battery is placed under a laser and scanned for 5 seconds with an ultraviolet laser with a power of 5W and a wavelength of 320~400nm to obtain a grooved battery; (3) Reverse electroplating with acidic oxide solution: The grooved battery is placed in an acidic oxide solution, with the grooved battery as the anode and the titanium mesh electrode as the cathode, and the current density is controlled at 2A / dm 2Electroplating for 3 minutes, then removing, rinsing with deionized water, and drying with nitrogen to obtain an acid-treated battery; wherein, the weight ratio of each component in the acidic oxidation solution is hydrochloric acid: hydrogen peroxide: sodium chloride: deionized water = 1:1.5:0.2:25; (4) Alkaline oxidation solution reverse electroplating: the acid-treated battery is placed in the alkaline oxidation solution, with the acid-treated battery as the anode and the titanium mesh electrode as the cathode, and the current density is controlled at 1A / dm 2 Electroplating for 5 minutes, then removing, rinsing with deionized water, and drying with nitrogen to obtain an alkaline-treated battery; wherein, the weight ratio of each component in the alkaline oxidation solution is ammonia: hydrogen peroxide: sodium hydroxide: deionized water = 1:1.3:0.3:30; (5) Preparation of high-entropy alloy electrode: The alkaline-treated battery is placed in a high-entropy alloy electroplating solution, with the alkaline-treated battery as the cathode and the platinum electrode as the anode, and the current density is controlled at 3A / dm 2 Electroplating for 5 minutes, then removing, rinsing with deionized water, drying with nitrogen, and then placing in a vacuum oven for annealing at 300℃ for 5 hours, followed by cooling, yields a high-entropy alloy electrode for use in tunnel oxide layer passivation contact batteries. The components and concentrations in the high-entropy alloy electroplating solution are as follows: cobalt sulfate 30g / L, nickel sulfate 30g / L, chromium trichloride 30g / L, stannous chloride 30g / L, zinc sulfate 30g / L, trisodium citrate 150g / L, glycine 60g / L, ammonium sulfate 150g / L, naphthol sulfonic acid 2g / L, with the pH adjusted to 2-3 using 1M dilute sulfuric acid aqueous solution, and the remainder being deionized water.

[0025] Referring to standard GB / T 43058 2023 "Ammonia Corrosion Test for Photovoltaic Modules", the corrosion resistance of the high-entropy alloy electrode was tested. Referring to standard ASTM D 3359 "Standard Test Methods for Rating Adhesion by Tape Test", the adhesion between the high-entropy alloy electrode and the tunnel oxide passivated contact cell after the ammonia corrosion test was tested, and the result was rated as 5B (100% no peeling).

[0026] Referring to standard ASTM B193, "Standard Test Method for Resistivity of Electrical Conductor Materials," the resistivity of the high-entropy alloy electrode was measured to be 2.27 μΩ·cm. Example 3

[0027] (1) Cleaning the battery: The tunneling oxide passivated contact battery is rinsed with deionized water, ethanol and acetone in sequence, and then placed in a vacuum oven and dried at 55°C to obtain a clean tunneling oxide passivated contact battery; (2) Laser grooving: The clean tunneling oxide passivated contact battery is placed under a laser and scanned for 4 seconds with an ultraviolet laser with a power of 5W and a wavelength of 320~400nm to obtain a grooved battery; (3) Reverse electroplating with acidic oxide solution: The grooved battery is placed in an acidic oxide solution, with the grooved battery as the anode and the titanium mesh electrode as the cathode, and the current density is controlled at 1.5A / dm. 2 Electroplating for 3 minutes, then removing, rinsing with deionized water, and drying with nitrogen to obtain an acid-treated battery; wherein, the weight ratio of each component in the acidic oxidation solution is hydrochloric acid: hydrogen peroxide: sodium chloride: deionized water = 1:1.3:0.15:24; (4) Alkaline oxidation solution reverse electroplating: the acid-treated battery is placed in the alkaline oxidation solution, with the acid-treated battery as the anode and the titanium mesh electrode as the cathode, and the current density is controlled at 0.8A / dm 2 Electroplating for 4 minutes, then removing, rinsing with deionized water, and drying with nitrogen to obtain an alkaline-treated battery; wherein, the weight ratio of each component in the alkaline oxidation solution is ammonia: hydrogen peroxide: sodium hydroxide: deionized water = 1:1.1:0.25:28; (5) Preparation of high-entropy alloy electrode: The alkaline-treated battery is placed in a high-entropy alloy electroplating solution, with the alkaline-treated battery as the cathode and the platinum electrode as the anode, and the current density is controlled at 2.5A / dm 2 Electroplating for 8 minutes, then removing, rinsing with deionized water, drying with nitrogen, and then placing in a vacuum oven for annealing at 320℃ for 4 hours, followed by cooling, yields a high-entropy alloy electrode for use in tunnel oxide layer passivation contact batteries. The components and concentrations in the high-entropy alloy electroplating solution are as follows: cobalt sulfate 25g / L, nickel sulfate 25g / L, chromium trichloride 25g / L, stannous chloride 25g / L, zinc sulfate 25g / L, trisodium citrate 130g / L, glycine 50g / L, ammonium sulfate 120g / L, naphthol sulfonic acid 1.5g / L, with the pH adjusted to 2-3 using 1M dilute sulfuric acid aqueous solution, and the remainder being deionized water.

[0028] Referring to standard GB / T 43058 2023 "Ammonia Corrosion Test for Photovoltaic Modules", the corrosion resistance of the high-entropy alloy electrode was tested. Referring to standard ASTM D 3359 "Standard Test Methods for Rating Adhesion by Tape Test", the adhesion between the high-entropy alloy electrode and the tunnel oxide passivated contact cell after the ammonia corrosion test was tested, and the result was rated as 5B (100% no peeling).

[0029] Referring to standard ASTM B193, "Standard Test Method for Resistivity of Electrical Conductor Materials," the resistivity of the high-entropy alloy electrode was measured to be 2.39 μΩ·cm. Example 4

[0030] (1) Cleaning the battery: The tunneling oxide passivated contact battery is rinsed with deionized water, ethanol and acetone in sequence, and then placed in a vacuum oven and dried at 60°C to obtain a clean tunneling oxide passivated contact battery; (2) Laser grooving: The clean tunneling oxide passivated contact battery is placed under a laser and scanned for 5 seconds with an ultraviolet laser with a power of 5W and a wavelength of 320~400nm to obtain a grooved battery; (3) Reverse electroplating with acidic oxide solution: The grooved battery is placed in an acidic oxide solution, with the grooved battery as the anode and the titanium mesh electrode as the cathode, and the current density is controlled at 2A / dm 2 Electroplating for 3 minutes, then removing, rinsing with deionized water, and drying with nitrogen to obtain an acid-treated battery; wherein, the weight ratio of each component in the acidic oxidation solution is hydrochloric acid: hydrogen peroxide: sodium chloride: deionized water = 1:1.5:0.1:20; (4) Alkaline oxidation solution reverse electroplating: the acid-treated battery is placed in the alkaline oxidation solution, with the acid-treated battery as the anode and the titanium mesh electrode as the cathode, and the current density is controlled at 1A / dm 2 Electroplating for 5 minutes, then removing, rinsing with deionized water, and drying with nitrogen to obtain an alkaline-treated battery; wherein, the weight ratio of each component in the alkaline oxidation solution is ammonia: hydrogen peroxide: sodium hydroxide: deionized water = 1:1.3:0.2:27; (5) Preparation of high-entropy alloy electrode: The alkaline-treated battery is placed in a high-entropy alloy electroplating solution, with the alkaline-treated battery as the cathode and the platinum electrode as the anode, and the current density is controlled at 3A / dm 2 Electroplating for 8 minutes, then removing, rinsing with deionized water, drying with nitrogen, and then placing in a vacuum oven for annealing at 350℃ for 4 hours, followed by cooling, yields a high-entropy alloy electrode for use in tunnel oxide layer passivation contact batteries. The components and concentrations in the high-entropy alloy electroplating solution are as follows: cobalt sulfate 28g / L, nickel sulfate 26g / L, chromium trichloride 27g / L, stannous chloride 25g / L, zinc sulfate 27g / L, trisodium citrate 110g / L, glycine 45g / L, ammonium sulfate 140g / L, naphthol sulfonic acid 1.8g / L. The pH is adjusted to 2-3 with 1M dilute sulfuric acid aqueous solution, and the remainder is deionized water.

[0031] Referring to standard GB / T 43058 2023 "Ammonia Corrosion Test for Photovoltaic Modules", the corrosion resistance of the high-entropy alloy electrode was tested. Referring to standard ASTM D 3359 "Standard Test Methods for Rating Adhesion by Tape Test", the adhesion between the high-entropy alloy electrode and the tunnel oxide passivated contact cell after the ammonia corrosion test was tested, and the result was rated as 5B (100% no peeling).

[0032] Referring to standard ASTM B193, "Standard Test Method for Resistivity of Electrical Conductor Materials," the resistivity of the high-entropy alloy electrode was measured to be 2.58 μΩ·cm. Example 5

[0033] (1) Cleaning the battery: The tunneling oxide passivated contact battery is rinsed with deionized water, ethanol and acetone in sequence, and then placed in a vacuum oven and dried at 55°C to obtain a clean tunneling oxide passivated contact battery; (2) Laser grooving: The clean tunneling oxide passivated contact battery is placed under a laser and scanned for 3 seconds with an ultraviolet laser with a power of 5W and a wavelength of 320~400nm to obtain a grooved battery; (3) Reverse electroplating with acidic oxide solution: The grooved battery is placed in an acidic oxide solution, with the grooved battery as the anode and the titanium mesh electrode as the cathode, and the current density is controlled at 1.8A / dm 2 Electroplating for 3 minutes, then removing, rinsing with deionized water, and drying with nitrogen to obtain an acid-treated battery; wherein, the weight ratio of each component in the acidic oxidation solution is hydrochloric acid: hydrogen peroxide: sodium chloride: deionized water = 1:1.4:0.17:24; (4) Alkaline oxidation solution reverse electroplating: the acid-treated battery is placed in the alkaline oxidation solution, with the acid-treated battery as the anode and the titanium mesh electrode as the cathode, and the current density is controlled at 0.8A / dm 2 Electroplating for 4 minutes, then removing, rinsing with deionized water, and drying with nitrogen to obtain an alkaline-treated battery; wherein, the weight ratio of each component in the alkaline oxidation solution is ammonia: hydrogen peroxide: sodium hydroxide: deionized water = 1:1.1:0.26:26; (5) Preparation of high-entropy alloy electrode: The alkaline-treated battery is placed in a high-entropy alloy electroplating solution, with the alkaline-treated battery as the cathode and the platinum electrode as the anode, and the current density is controlled at 2.2A / dm. 2Electroplating for 9 minutes, then removing, rinsing with deionized water, drying with nitrogen, and then placing in a vacuum oven for annealing at 350℃ for 3 hours, followed by cooling, yields a high-entropy alloy electrode for tunnel oxide layer passivation contact batteries. The components and concentrations in the high-entropy alloy electroplating solution are as follows: cobalt sulfate 23g / L, nickel sulfate 26g / L, chromium trichloride 21g / L, stannous chloride 24g / L, zinc sulfate 24g / L, trisodium citrate 130g / L, glycine 55g / L, ammonium sulfate 140g / L, naphthol sulfonic acid 2g / L, with the pH adjusted to 2-3 using 1M dilute sulfuric acid aqueous solution, and the remainder being deionized water.

[0034] Referring to standard GB / T 43058 2023 "Ammonia Corrosion Test for Photovoltaic Modules", the corrosion resistance of the high-entropy alloy electrode was tested. Referring to standard ASTM D 3359 "Standard Test Methods for Rating Adhesion by Tape Test", the adhesion between the high-entropy alloy electrode and the tunnel oxide passivated contact cell after the ammonia corrosion test was tested, and the result was rated as 5B (100% no peeling).

[0035] Referring to standard ASTM B193, "Standard Test Method for Resistivity of Electrical Conductor Materials," the resistivity of the high-entropy alloy electrode was measured to be 2.46 μΩ·cm. (Comparative Example 1)

[0036] In Example 1, the acidic oxide solution reverse electroplating in step (3) and the alkaline oxide solution reverse electroplating in step (4) are removed, while other parameters remain unchanged. Specifically, the following steps are taken: (1) Cleaning the battery: The tunneling oxide layer passivated contact battery is rinsed with deionized water, ethanol, and acetone in sequence, and then placed in a vacuum oven and dried at 50°C to obtain a clean tunneling oxide layer passivated contact battery; (2) Laser grooving: The clean tunneling oxide layer passivated contact battery is placed under a laser and scanned for 3 seconds with an ultraviolet laser with a power of 5W and a wavelength of 320~400nm to obtain a grooved battery; (3) Preparation of high-entropy alloy electrode: The grooved battery is placed in a high-entropy alloy electroplating solution, with an alkaline-treated battery as the cathode and a platinum electrode as the anode, and the current density is controlled at 2A / dm. 2Electroplating for 10 minutes, then removing, rinsing with deionized water, drying with nitrogen, and then placing in a vacuum oven for annealing at 350℃ for 3 hours, followed by cooling, yields a high-entropy alloy electrode for use in tunnel oxide layer passivation contact batteries. The components and concentrations in the high-entropy alloy electroplating solution are as follows: cobalt sulfate 20g / L, nickel sulfate 20g / L, chromium trichloride 20g / L, stannous chloride 20g / L, zinc sulfate 20g / L, trisodium citrate 100g / L, glycine 40g / L, ammonium sulfate 100g / L, naphthol sulfonic acid 1g / L, pH adjusted to 2-3 with 1M dilute sulfuric acid aqueous solution, with the remainder being deionized water.

[0037] The high-entropy alloy electrode prepared in Comparative Example 1 for tunnel oxide passivation contact cells is discontinuous, and there is no conductivity between the electrode lines, resulting in electrode fabrication failure.

[0038] According to the standard ASTM D 3359 "Standard Test Methods for Rating Adhesion by Tape Test", the high-entropy electrode prepared in Comparative Example 1 was tested. Approximately 50% of the electrode detached, and the adhesion was rated as 1B.

Claims

1. A method for preparing a high-entropy alloy electrode for a tunnel oxide passivated contact battery, characterized in that: (1) Cleaning the battery: The tunneling oxide passivated contact battery is rinsed with deionized water, ethanol and acetone in sequence, and then placed in a vacuum oven and dried at 50~60℃ to obtain a clean tunneling oxide passivated contact battery; (2) Laser grooving: The clean tunneling oxide passivated contact battery is placed under a laser and scanned for 3~5 seconds with an ultraviolet laser with a power of 5W and a wavelength of 320~400nm to obtain a grooved battery; (3) Reverse electroplating with acidic oxide solution: The grooved battery is placed in an acidic oxide solution, with the grooved battery as the anode and the titanium mesh electrode as the cathode, and the current density is controlled at 1~2A / dm 2 Electroplating for 2-3 minutes, then removing, rinsing with deionized water, and drying with nitrogen to obtain an acid-treated battery; wherein, the weight ratio of each component in the acidic oxidation solution is hydrochloric acid: hydrogen peroxide: sodium chloride: deionized water = 1: (1-1.5): (0.1-0.2): (20-25); (4) Alkaline oxidation solution reverse electroplating: place the acid-treated battery in the alkaline oxidation solution, with the acid-treated battery as the anode and the titanium mesh electrode as the cathode, and control the current density to be 0.5-1A / dm 2 Electroplating for 3-5 minutes, then removing, rinsing with deionized water, and drying with nitrogen to obtain an alkaline-treated battery; wherein, the weight ratio of each component in the alkaline oxidation solution is ammonia: hydrogen peroxide: sodium hydroxide: deionized water = 1: (1-1.3): (0.2-0.3): (25-30); (5) Preparation of high-entropy alloy electrode: The alkaline-treated battery is placed in a high-entropy alloy electroplating solution, with the alkaline-treated battery as the cathode and the platinum electrode as the anode, and the current density is controlled at 2-3 A / dm 2 Electroplating for 5-10 minutes, then removing, rinsing with deionized water, drying with nitrogen, and then placing in a vacuum oven for annealing at 300-350℃ for 3-5 hours, followed by cooling, yields a high-entropy alloy electrode for use in tunnel oxide layer passivation contact batteries. The components and concentrations in the high-entropy alloy electroplating solution are as follows: cobalt sulfate 20-30 g / L, nickel sulfate 20-30 g / L, chromium trichloride 20-30 g / L, stannous chloride 20-30 g / L, zinc sulfate 20-30 g / L, trisodium citrate 100-150 g / L, glycine 40-60 g / L, ammonium sulfate 100-150 g / L, naphthol sulfonic acid 1-2 g / L, with the pH adjusted to 2-3 using a 1M dilute sulfuric acid aqueous solution, and the remainder being deionized water.

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