Barrier-enhanced composite current collector, method of making the same, electrode, and battery

Abstract

The present disclosure provides a barrier-enhanced composite current collector, a preparation method thereof, an electrode and a battery. The barrier-enhanced composite current collector comprises a polymer substrate, a barrier layer and a metal conductive layer; the barrier layer covers at least one side surface of the polymer substrate, and the metal conductive layer is arranged on the side of the barrier layer away from the polymer substrate; and the material of the barrier layer comprises an amorphous alloy material. The amorphous alloy material is arranged between the polymer substrate and the metal conductive layer, which can effectively block the electrolyte from penetrating while basically not affecting the mechanical properties and conductive properties of the barrier-enhanced composite current collector, thereby improving the long-term service life of the barrier-enhanced composite current collector.

Description

Technical Field

[0001] This invention relates to the field of battery technology, and in particular to a barrier-enhanced composite current collector, its preparation method, electrode, and battery. Background Technology

[0002] Current collectors are crucial components in batteries, serving not only to support the active electrode materials but also to transfer electrons between them and the external circuitry. Current collectors are typically made of metallic materials, which not only increases their manufacturing cost but also results in them comprising a significant weight proportion of the battery, leading to a lower specific energy of the battery.

[0003] Composite current collectors typically consist of a substrate film and a metal film layer on top of it. They can reduce the overall mass of the current collector while maintaining both mechanical and electrical properties, making them a promising product. However, during long-term use, composite current collectors suffer from reduced adhesion between the metal film layer and the substrate, eventually leading to detachment and a shorter lifespan. This limits their further application. Summary of the Invention

[0004] Therefore, in order to improve the long-term service life of composite current collectors, it is necessary to provide a barrier-reinforced composite current collector.

[0005] According to some embodiments of the present disclosure, a barrier-enhanced composite current collector is provided, which includes: a polymer substrate, a barrier layer and a metal conductive layer;

[0006] The barrier layer covers at least one side surface of the polymer substrate, the conductive metal layer is disposed on the side of the barrier layer away from the polymer substrate, and the material of the barrier layer includes an amorphous alloy material.

[0007] In some examples of this embodiment, the amorphous alloy material is selected from one or more of nickel-phosphorus alloys, nickel-boron alloys, cobalt-phosphorus alloys, cobalt-boron alloys, and chromium-phosphorus alloys.

[0008] In some embodiments of this disclosure, the mass content of non-metallic elements in the amorphous alloy material is 1% to 6%.

[0009] In some embodiments of this disclosure, the thickness of the barrier layer is 200 nm to 900 nm.

[0010] In some embodiments of this disclosure, the sheet resistance of the barrier layer is ≤2Ω / □.

[0011] In some embodiments of this disclosure, an adhesion enhancement layer is further included, which is disposed between the polymer substrate and the barrier layer, and the adhesion enhancement layer is formed by polymerizing a film from raw materials including acrylic oligomers and epoxy resins.

[0012] In some embodiments of this disclosure, the metallic conductive layer comprises copper or aluminum.

[0013] In some embodiments of this disclosure, the thickness of the metal conductive layer is 800 nm to 2000 nm; and / or,

[0014] The thickness of the polymer substrate is 1 μm to 4 μm.

[0015] According to some embodiments of this disclosure, a method for preparing the above-mentioned barrier-reinforced composite current collector is also provided, which includes the following steps:

[0016] The amorphous alloy material is prepared on the polymer substrate by chemical plating to serve as the barrier layer;

[0017] The conductive metal layer is prepared on the barrier layer.

[0018] In some embodiments of this disclosure, the plating solution used to prepare the amorphous alloy material includes: a main salt, a main salt reducing agent, a stabilizer, and a brightener. The main salt includes one or more of nickel, cobalt, and chromium. The main salt reducing agent contains one or more of boron and phosphorus. The main salt reducing agent is used to reduce the main salt, so that the non-metallic elements therein are co-deposited with the metallic elements in the main salt to form the amorphous alloy material.

[0019] In some embodiments of this disclosure, the brightening agent comprises coumarin at a mass concentration of 8 mg / L to 12 mg / L and sodium dodecyl sulfonate at a mass concentration of 1 mg / L to 3 mg / L.

[0020] In some embodiments of this disclosure, the stabilizer includes potassium iodate at a mass concentration of 18 mg / L to 22 mg / L and DL-cysteine ​​at a mass concentration of 2 mg / L to 4 mg / L.

[0021] In some embodiments of this disclosure, the main salt includes one or more of nickel sulfate, nickel sulfide, and nickel aminosulfonate, and the mass concentration of the main salt is 18 g / L to 30 g / L.

[0022] In some embodiments of this disclosure, the reducing agent includes one or more of sodium hypophosphite and dimethylamine borane, and the mass concentration of the reducing agent is 5 g / L to 30 g / L.

[0023] In some embodiments of this disclosure, the plating solution further includes a complexing agent selected from one or more of sodium citrate, glycine, succinic acid, ethylenediaminetetraacetic acid, and lactic acid, wherein the mass concentration of the complexing agent is 15 g / L to 30 g / L.

[0024] In some embodiments of this disclosure, the plating solution further includes an accelerator selected from one or more of malonic acid, succinic acid, glutaric acid, adipic acid, and glycine, and the mass concentration of the accelerator is 16 g / L to 20 g / L.

[0025] In some embodiments of this disclosure, the pH value of the plating solution is 8.5 to 9.5.

[0026] In some embodiments of this disclosure, the metal conductive layer is prepared by electroplating. Before preparing the barrier layer, the method further includes: preparing a catalyst on the polymer substrate for catalyzing the formation of the metal conductive layer.

[0027] According to some other embodiments of this disclosure, an electrode is also provided, which includes a current collector and an electrode active material disposed on the current collector, wherein the current collector is a barrier-reinforced composite current collector according to any of the above embodiments.

[0028] According to some other embodiments of this disclosure, a battery is also provided, which includes a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode and the negative electrode are disposed opposite to each other, and the electrolyte is disposed between the positive electrode and the negative electrode, and one or both of the positive electrode and the negative electrode are electrodes as described in the above embodiments.

[0029] This disclosure provides a novel approach to barrier-reinforced composite current collectors by introducing an amorphous alloy material as a barrier layer between a polymer substrate and a metallic conductive layer. The amorphous alloy material itself possesses good conductivity and exhibits strong adhesion to the metallic conductive layer. More importantly, the amorphous alloy material is typically composed of a cellular structure at the microscopic level, forming a homogeneous single-phase system free from structural defects such as grain boundaries and dislocations, as well as chemical segregation issues. It also avoids intergranular corrosion and stress corrosion, effectively preventing electrolyte permeation. Therefore, placing the amorphous alloy material between the polymer substrate and the metallic conductive layer effectively blocks electrolyte permeation without significantly affecting the mechanical and conductive properties of the barrier-reinforced composite current collector, thereby improving its long-term service life. Attached Figure Description

[0030] Figure 1 A schematic diagram of a barrier-reinforced composite current collector is shown.

[0031] Figure 2 A schematic diagram illustrating the steps of a method for preparing a barrier-reinforced composite current collector is shown.

[0032] Figure 3 A schematic diagram showing the adhesion test results of the barrier-reinforced composite current collector of Example 1.1 after immersion in electrolyte for 72 hours is shown.

[0033] Figure 4 A schematic diagram showing the adhesion test results of the barrier-reinforced composite current collector of Example 1.1 after immersion in electrolyte for 168 hours is shown.

[0034] Figure 5 A schematic diagram of the adhesion test results of the barrier-reinforced composite current collector of Comparative Example 1 after immersion in electrolyte for 72 hours is shown.

[0035] Figure 6 A schematic diagram of the adhesion test results of the barrier-reinforced composite current collector of Comparative Example 1 after 168 hours of immersion in electrolyte is shown.

[0036] Figure 7 The morphology of the barrier layers prepared in Comparative Example 3 and Example 1.1 is shown under a scanning electron microscope, where the left image is the barrier layer in Comparative Example 3 and the right image is the barrier layer in Example 1.1.

[0037] The reference numerals and their meanings in the accompanying drawings are as follows:

[0038] 100. Polymer substrate; 110. Adhesion reinforcement layer; 120. Barrier layer; 130. Metal conductive layer. Detailed Implementation

[0039] To facilitate understanding of the present invention, a more comprehensive description is provided below. Preferred embodiments of the invention are shown herein. However, the invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the invention.

[0040] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification of this invention is for the purpose of describing particular embodiments only and is not intended to limit the invention. The term “and / or” as used herein includes any and all combinations of one or more of the associated listed items. The term “more” as used herein includes two or more items. The term “above a certain number” as used herein should be understood as a number and a range greater than a certain number.

[0041] In traditional barrier-reinforced composite current collectors, the metal film layer is typically a copper or aluminum layer, usually prepared by electroplating or sputtering. Although the metal film layer initially adheres relatively stably to the substrate film, it inevitably detaches gradually after being assembled into a battery. This disclosure reveals that defects are unavoidable in the crystal lattice of the prepared metal film layer, resulting in tiny gaps. During actual use, small molecules in the electrolyte can easily penetrate these gaps and contact the substrate film, causing swelling. On one hand, the adhesion between the swollen substrate film and the coating decreases; on the other hand, the swollen substrate film undergoes localized deformation, leading to significant stress and eventual peeling of the metal film layer.

[0042] In order to improve the long-term service life of the barrier-reinforced composite current collector without substantially affecting its mechanical and electrical properties, this disclosure provides a barrier-reinforced composite current collector, which includes: a polymer substrate, a barrier layer, and a metal conductive layer; the barrier layer covers at least one side surface of the polymer substrate, the metal conductive layer is disposed on the side surface of the barrier layer away from the polymer substrate, and the material of the barrier layer includes an amorphous alloy material.

[0043] This disclosure provides a novel approach to barrier-reinforced composite current collectors by introducing an amorphous alloy material as a barrier layer between a polymer substrate and a metallic conductive layer. The amorphous alloy material itself possesses good conductivity and exhibits strong adhesion to the metallic conductive layer. More importantly, the amorphous alloy material is typically composed of a cellular structure at the microscopic level, forming a homogeneous single-phase system free from structural defects such as grain boundaries and dislocations, as well as chemical segregation issues. It also avoids intergranular corrosion and stress corrosion, effectively preventing electrolyte permeation. Therefore, placing the amorphous alloy material between the polymer substrate and the metallic conductive layer effectively blocks electrolyte permeation without significantly affecting the mechanical and conductive properties of the barrier-reinforced composite current collector, thereby improving its long-term service life.

[0044] Figure 1 A schematic diagram of the barrier-reinforced composite current collector of this disclosure is shown. (Refer to...) Figure 1 As shown, the barrier-enhanced composite current collector includes a polymer substrate 100, a barrier layer 120, and a metal conductive layer 130. There are two barrier layers 120, each covering one of the opposite surfaces of the polymer substrate 100. There are also two metal conductive layers 130, each disposed on the side of the two barrier layers 120 away from the polymer substrate 100.

[0045] In this embodiment, the amorphous alloy material exhibits short-range order and long-range disorder in its microstructure. In some examples of this embodiment, the amorphous alloy material is selected from one or more of nickel-phosphorus alloys, nickel-boron alloys, cobalt-phosphorus alloys, cobalt-boron alloys, and chromium-phosphorus alloys. It is understood that the aforementioned nickel-phosphorus alloys and cobalt-phosphorus alloys may also contain other metallic elements, as long as they can form an amorphous alloy material. For example, a nickel-phosphorus alloy contains nickel and phosphorus, and may also contain copper and / or manganese. Similarly, a cobalt-phosphorus alloy contains cobalt and phosphorus, and may also contain copper and / or manganese.

[0046] In some examples of this embodiment, the amorphous alloy material can be one or more of nickel-phosphorus alloys and nickel-boron alloys. The nickel-phosphorus alloy may further include copper, i.e., a nickel-copper-phosphorus alloy, or it may include manganese, i.e., a nickel-manganese-phosphorus alloy. Compared to other alloys, the electrode potential of the nickel alloy is lower than that of copper. When the material of the conductive metal layer includes copper, the barrier layer 120 can also contact the conductive metal layer 130 to form a galvanic cell. In this case, the nickel alloy corrodes preferentially over copper, thus protecting the conductive metal layer 130.

[0047] In some examples of this embodiment, when an amorphous alloy material is used as the barrier layer 120, the surface of the barrier layer 120 should be intact and free of cracks; otherwise, it will be difficult to achieve an effective blocking effect. In actual preparation, a more suitable preparation method can be selected to ensure that the surface of the prepared amorphous alloy material is intact and free of cracks.

[0048] In some examples of this embodiment, the barrier layer 120 should be able to adhere stably to the polymer substrate 100; otherwise, the barrier layer 120 will not be able to adhere to the polymer substrate 100, which will also cause the metal conductive layer 130 located on the barrier layer 120 to not adhere stably.

[0049] It is understood that the metal conductive layer 130 can be prepared by vapor deposition or electroplating. In some examples of this embodiment, the metal conductive layer 130 is prepared by electroplating. Compared with vapor deposition, electroplating is more efficient and has a lower manufacturing cost, making it suitable for large-scale production.

[0050] In some examples of this embodiment, the material of the metal conductive layer 130 may include copper or aluminum.

[0051] In order to minimize the impact of the barrier layer 120 on subsequent electroplating, in some examples of this embodiment, the sheet resistance of the barrier layer 120 is ≤2Ω / □. This ensures the uniformity of the metal conductive layer 130, thereby improving the resistance of the metal conductive layer 130 to electrolyte corrosion. If the sheet resistance of the barrier layer 120 is >2Ω / □, the electroplated metal conductive layer 130 will have obvious non-uniformity, or it will be difficult to prepare the metal conductive layer 130 on the barrier layer 120 by electroplating.

[0052] The barrier-reinforced composite current collector provided in this disclosure can be a thin current collector or a thick current collector. The total thickness of the composite current collector can be 1 μm to 50 μm, and further, the total thickness of the composite current collector can be 3 μm to 20 μm, which can be selected according to actual needs.

[0053] In this embodiment, when the total thickness of the composite current collector is high, for example, when the total thickness of the composite current collector is above 6 μm, the barrier layer 120 can also have a high thickness, for example, the thickness of the barrier layer 120 is 1 μm to 5 μm. A higher thickness is more conducive to controlling the sheet resistance of the barrier layer 120 to below 2 Ω / □.

[0054] Furthermore, the barrier-enhanced composite current collector provided in this embodiment can be an ultrathin current collector, for example, the total thickness of the current collector can be less than 6 μm. However, in the actual fabrication process, there are also more new technical problems to be faced when fabricating an ultrathin current collector. Specifically, when the total thickness of the composite current collector is less than 6 μm, since both the polymer substrate 100 and the metal conductive layer 130 need to occupy a considerable thickness, the thickness of the barrier layer 120 is relatively limited, which leads to a higher sheet resistance of the barrier layer 120, a problem that is difficult to overcome.

[0055] In some examples of this embodiment, the thickness of the metal conductive layer 130 is 800 nm to 2000 nm.

[0056] In some examples of this embodiment, the thickness of the polymer substrate 100 is 1 μm to 4 μm.

[0057] In some examples of this embodiment, the thickness of the barrier layer 120 is 200 nm to 900 nm.

[0058] In this embodiment, the amorphous alloy material contains non-metallic elements, such as boron and phosphorus. To overcome the problem of high sheet resistance in the barrier layer 120, in some examples of this embodiment, the mass content of non-metallic elements in the amorphous alloy material is 1% to 6%. Maintaining a mass content of non-metallic elements above 1% is beneficial for obtaining superior barrier performance, resulting in a longer service life for the barrier-reinforced composite current collector. Maintaining a mass content of non-metallic elements below 6% is to obtain better conductivity while still meeting the barrier performance requirements. This is beneficial for the barrier layer 120 to meet the requirement of a sheet resistance ≤2Ω / □ even when it is relatively thin.

[0059] In some examples of this embodiment, the material of the polymer substrate 100 may be selected from one or more of polypropylene, polyethylene terephthalate, and polyimide. Further, the material of the polymer substrate 100 is polyimide, in which case the adhesion between the polymer substrate 100 and the barrier layer 120 is stronger, and the barrier layer 120 can be in direct contact with the polymer substrate 100.

[0060] Reference Figure 1 As shown, in some examples of this embodiment, the composite current collector further includes an adhesion enhancement layer 110, which is disposed between the polymer substrate 100 and the barrier layer 120. The adhesion enhancement layer 110 is formed by polymerizing a film from raw materials including acrylic oligomers and epoxy resin. There are two adhesion enhancement layers 110 corresponding to the two barrier layers 120. The function of the adhesion enhancement layer 110 is to improve the adhesion between the polymer substrate 100 and the barrier layer 120, thereby further extending the service life of the barrier-enhanced composite current collector. Furthermore, the composite current collector with the adhesion enhancement layer 110 can also overcome the problem that the barrier layer 120 easily detaches from the polymer substrate 100, which includes polypropylene and polyethylene terephthalate.

[0061] It is understood that in this embodiment, the barrier layer 120 effectively blocks electrolyte molecules, thereby slowing down the rate of decrease in adhesion between the polymer substrate 100 and the barrier layer 120. The adhesion enhancement layer 110 further enhances the adhesion between the polymer substrate 100 and the barrier layer 120. The two layers complement each other and work synergistically to significantly extend the service life of the barrier-enhanced composite current collector.

[0062] Furthermore, this disclosure also provides an electrode comprising a current collector and an electrode active material disposed on the current collector, wherein the current collector is a barrier-reinforced composite current collector according to the above embodiments. The electrode active material can be a positive electrode active material of a lithium-ion battery or a negative electrode active material of a lithium-ion battery.

[0063] Furthermore, this disclosure also provides a battery comprising a positive electrode, a negative electrode, and an electrolyte, wherein the positive and negative electrodes are disposed opposite to each other, and the electrolyte is disposed between the positive and negative electrodes, and one or both of the positive and negative electrodes are electrodes as described in the above embodiments. Optionally, the battery may be a lithium-ion battery.

[0064] This disclosure also provides a method for preparing the barrier-enhanced composite current collector in the above embodiments, which includes the following steps: preparing an amorphous alloy material on a polymer substrate by chemical plating to serve as a barrier layer; and electroplating a conductive metal layer on the barrier layer.

[0065] To facilitate understanding of the preparation method of the barrier-reinforced composite current collector in this embodiment, refer to... Figure 2 As shown, a method for preparing a barrier-enhanced composite current collector includes steps S1 to S5.

[0066] Step S1: Provide a polymer substrate.

[0067] In some examples of this embodiment, the provided polymer substrate may include one or more of polyethylene terephthalate, polypropylene, and polyimide. Alternatively, the polymer substrate may be selected from other suitable polymer materials.

[0068] In some examples of this embodiment, the provided polymer substrate may include one or more of polyethylene terephthalate and polypropylene.

[0069] In some examples of this embodiment, a pre-cleaning step of the polymer substrate is also included. Optionally, the pre-cleaning agent used to pre-clean the polymer substrate is an organic solvent, such as a ketone, alcohol, or ester solvent. Optionally, the pre-cleaning agent may include one or more of acetone, ethanol, isopropanol, and ethyl lactate.

[0070] Optionally, the pre-cleaning step of the polymer substrate can take 1 to 10 minutes. After pre-cleaning the polymer substrate, it can also be dried at 50°C to 90°C to remove residual organic solvents from the surface of the polymer substrate.

[0071] Step S2: Prepare an adhesion enhancement layer on the polymer substrate.

[0072] In some examples of this embodiment, the step of preparing an adhesion reinforcement layer on a polymer substrate includes: coating a reinforcement precursor material on the polymer substrate; drying the reinforcement precursor material to cure it; and immersing the cured reinforcement precursor material in a surfactant to obtain the adhesion reinforcement layer.

[0073] The reinforcing precursor materials include acrylic oligomers, epoxy resins, and dispersants. In the adhesive material layer, the mass content of acrylic oligomers is 18% to 30%, and the mass content of epoxy resins is 2% to 10%.

[0074] Optionally, in the step of drying the reinforcing precursor material, the drying temperature is controlled to be between 55°C and 85°C. The purpose of drying is to remove the solvent from the reinforcing precursor material and to cure the acrylic oligomers and epoxy resin therein. It is understood that the acrylic oligomers and epoxy resin can also be cured by other suitable methods.

[0075] Optionally, in the step of soaking and curing the reinforcing precursor material with a surfactant, the processing temperature is controlled at 30℃ to 60℃, and the processing time is controlled at 3 min to 10 min. The purpose of soaking and curing the reinforcing precursor material with a surfactant is to improve the adsorption force on the surface of the formed adhesion reinforcement layer, so as to facilitate its bonding with the subsequently prepared barrier layer, etc.

[0076] The inventors of this disclosure have discovered through research that the reinforcing precursor material possesses permeability and wettability to the polymer substrate, facilitating the penetration of the material into the polymer substrate as much as possible. The resulting adhesion reinforcement layer, after curing, exhibits extremely high bonding strength with the polymer substrate. Furthermore, after treatment with a surfactant, this graft copolymer compound demonstrates high bonding strength with the subsequently prepared barrier layer.

[0077] In some examples of this embodiment, before immersing the cured reinforcing precursor material in a surfactant solution, the step further includes ultrasonically cleaning the cured reinforcing precursor material. Optionally, the ultrasonic cleaning agent used for ultrasonic cleaning may include organic solvents, such as alcohols, ketones, and / or esters. Further optionally, the ultrasonic cleaning agent may include one or more of acetone, ethanol, isopropanol, and ethyl lactate.

[0078] Optionally, during the ultrasonic cleaning step, the cleaning temperature can be controlled to be 20℃~50℃ and the cleaning time to be 1min~10min.

[0079] Although the adhesion enhancement layer can effectively improve the adhesion between the metal conductive layer and the polymer substrate, bubbling can still occur in the prepared metal conductive layer during the actual fabrication process, leading to the failure of the prepared metal conductive layer. The inventors discovered that pre-cleaning the cured reinforcing precursor material with a surfactant using ultrasonic cleaning can effectively avoid the bubbling problem in the metal conductive layer and improve the fabrication yield.

[0080] Step S3: Prepare a catalyst on the adhesion enhancement layer.

[0081] The catalyst is used to catalyze the formation of a metallic conductive layer.

[0082] In some examples of this embodiment, the step of preparing a catalyst on the adhesion enhancement layer includes: adsorbing a catalytic precursor material onto the surface of the adhesion enhancement layer, and forming the catalytic precursor material into a catalyst.

[0083] Optionally, the catalyst can be metal nanoparticles, such as one or more of copper, silver, and palladium particles. The catalytic precursor material can contain the corresponding metal ions, such as one or more of copper, silver, and palladium ions. For example, if the catalyst is palladium particles, the catalytic precursor material can contain palladium ions.

[0084] In some examples of this embodiment, adsorbing the catalytic precursor material onto the surface of the adhesion enhancement layer may include: activating the adhesion enhancement layer with an activator containing the catalytic precursor material. In this activator, the mass concentration of palladium ions may be 0.2 g / L to 0.5 g / L. During the activation process, the treatment temperature may be controlled at 40°C to 50°C, and the treatment time at 2 min to 10 min.

[0085] In some examples of this embodiment, the method of forming a catalyst from a catalytic precursor material may include reducing the catalytic precursor material with a precursor reducing agent to form a catalyst. Optionally, the reducing agent is selected from one or more of potassium borohydride, sodium borohydride, and dimethylformamide. The reduction of the catalytic precursor material with the precursor reducing agent can be carried out at room temperature. Optionally, the reduction time can be controlled to be between 30 s and 180 s.

[0086] Step S4: Prepare a barrier layer on the adhesion enhancement layer and the catalyst.

[0087] The barrier layer is made of amorphous alloy material.

[0088] In this embodiment, the amorphous alloy material is prepared by chemical plating to serve as a barrier layer.

[0089] In some examples of this embodiment, the plating solution used to prepare the amorphous alloy material includes: a main salt, a main salt reducing agent, a stabilizer, and a brightener. The main salt includes one or more of nickel, cobalt, and chromium. The main salt reducing agent contains one or more of boron and phosphorus. The main salt reducing agent is used to reduce the main salt, causing the non-metallic elements therein to co-deposit with the metallic elements in the main salt to form the amorphous alloy material. The stabilizer is used to control the electroplating speed and suppress spontaneous decomposition of the plating solution, while the brightener is used to refine the cellular structure of the coating, making the deposit more uniform and fine.

[0090] In this example, the prepared amorphous alloy material can be one or more of nickel-phosphorus alloy, nickel-boron alloy, cobalt-phosphorus alloy, cobalt-boron alloy, and chromium-phosphorus alloy.

[0091] In some examples of this embodiment, the main salt includes one or more of nickel sulfate, nickel sulfide, and nickel aminosulfonate, and the mass concentration of the main salt is 18 g / L to 30 g / L.

[0092] In some examples of this embodiment, the reducing agent includes one or more of sodium hypophosphite and dimethylamine borane, and the mass concentration of the reducing agent is 5 g / L to 30 g / L.

[0093] In some examples of this embodiment, the main salt includes one or more of nickel sulfate, nickel sulfide, and nickel aminosulfonate, and the mass concentration of the main salt is 18 g / L to 30 g / L.

[0094] In some examples of this embodiment, the reducing agent includes one or more of sodium hypophosphite and dimethylamine borane, and the mass concentration of the reducing agent is 5 g / L to 30 g / L.

[0095] The main salt and main salt reducing agent are used to provide the main elemental composition of the amorphous alloy material. For example, if the amorphous alloy material is a nickel-phosphorus alloy, the main salt may include a nickel salt, and the main salt reducing agent may include sodium hypophosphite. Sodium hypophosphite can reduce the nickel salt, and the phosphorus element therein is co-deposited with the nickel element to form a nickel-phosphorus alloy. As another example, if the amorphous alloy material is a nickel-boron alloy, the main salt may include a nickel salt, and the main salt reducing agent may include dimethylamineborane. Dimethylamineborane can reduce the nickel salt, and the boron element therein is co-deposited with the nickel element to form a nickel-boron alloy.

[0096] In actual preparation, the prepared barrier layer may suffer from stress mismatch with the polymer substrate. This can lead to cracking of the barrier layer. This not only causes the layer to lose its barrier function but also results in excessive sheet resistance and hinders the subsequent preparation of a uniform metallic conductive layer. Further research in this disclosure has revealed that using a brightener formulated with specific components and specific amounts can solve this problem. In some examples of this embodiment, the brightener includes coumarin at a mass concentration of 8 mg / L to 12 mg / L and sodium dodecyl sulfate at a mass concentration of 1 mg / L to 3 mg / L.

[0097] Experimental testing showed that, compared to other common brighteners, the brightener compounded as described above effectively improved the cracking problem of the barrier layer in this example. This is likely because the compounded brightener improves the growth pattern of the barrier layer, making its longitudinal growth in the thickness direction faster than its lateral growth in the planar direction. This results in a better fit between the barrier layer and the polymer substrate surface, thus reducing the internal stress of the barrier layer. This is beneficial for obtaining a complete, crack-free barrier layer.

[0098] It is understood that this embodiment provides an optional method for preparing the barrier layer. The barrier layer can also be prepared by other suitable methods, as long as a complete and crack-free barrier layer can be formed.

[0099] In some examples of this embodiment, the stabilizer may include one or more of benzotriazole, 2-mercaptobenzimidazole, DL-cysteine, potassium iodate, and 2-mercaptothiazole. Optionally, the stabilizer may include potassium iodate at a mass concentration of 18 mg / L to 22 mg / L and DL-cysteine ​​at a mass concentration of 2 mg / L to 4 mg / L, wherein the two components of this compound stabilizer promote each other and can improve the stability constant of the plating solution to 91.85%.

[0100] In some examples of this embodiment, the plating bath may further include a complexing agent, which is used to form stable complexes with the metal ions therein to control the plating rate. Optionally, the complexing agent may be one or more of sodium citrate, glycine, succinic acid, ethylenediaminetetraacetic acid, and lactic acid. Optionally, the mass concentration of the complexing agent is 15 g / L to 30 g / L.

[0101] In some embodiments of this example, the plating solution may further include a buffer. The buffer is used to maintain the pH stability of the plating solution. Optionally, the buffer may be one or more of ammonium chloride and boric acid.

[0102] In some embodiments of this example, the plating solution may further include an accelerator. The accelerator is used to accelerate the deposition rate of the amorphous alloy material. Optionally, the accelerator may be one or more of malonic acid, succinic acid, glutaric acid, adipic acid, and glycine. Optionally, the mass concentration of the accelerator is 16 g / L to 20 g / L.

[0103] In some embodiments of this example, the pH value of the plating solution is 8.5–9.5. It is understood that in the actual preparation process, the pH value of the plating solution can be controlled by a pH adjuster. The pH adjuster can be one or more of acetic acid, dilute sulfuric acid, ammonia, and sodium hydroxide.

[0104] It is understandable that different plating solutions may have different deposition rates. Therefore, the deposition time can be controlled to obtain amorphous alloy materials of corresponding thickness.

[0105] Step S5: Prepare a metal conductive layer on the barrier layer.

[0106] In some examples of this embodiment, the step of preparing the metal conductive layer includes: electroplating a metal film layer on the barrier layer, and passivating the metal film layer to form the metal conductive layer. The passivation process forms an anti-oxidation layer on the surface of the metal film layer.

[0107] In some examples of this embodiment, the metal film is electroplated based on a catalyst that has already been prepared.

[0108] It is understandable that different electroplating solutions can be selected for different metal film materials. For example, if copper is used as the metal film material, the electroplating solution may include copper sulfate and sulfuric acid. Optionally, the mass concentration of copper sulfate is 15 g / L to 50 g / L, and the volume concentration of sulfuric acid is 100 mL / L to 350 mL / L. The electroplating current and time can be selected accordingly based on the preparation rate and thickness of the metal film.

[0109] In some examples of this embodiment, a passivation solution can be used to passivate the metal film. Optionally, the passivation solution may include glucose and chromium trioxide. The passivation time is 3 to 5 minutes.

[0110] After passivation, the conductive metal layer can be dried.

[0111] It is understood that the required barrier-reinforced composite current collector can be formed through steps S1 to S5.

[0112] This disclosure further provides the following embodiments and comparative examples to demonstrate the advantages of the barrier-reinforced composite current collector provided herein.

[0113] Unless otherwise specified, all materials used in the embodiments can be purchased from the market.

[0114] Example 1.1

[0115] A 3 μm thick polyimide film was used as a polymer substrate, and it was ultrasonically cleaned in acetone for 5 min and then dried for later use.

[0116] The polymer substrate was immersed in a 4 mol / L sodium hydroxide solution for 3 min for modification treatment;

[0117] After cleaning, the polymer substrate was transferred to an activation solution containing palladium ions and immersed for 3 minutes, and then transferred to dimethylaminoborane for reduction.

[0118] A 200 nm thick nickel-phosphorus alloy was electrolessly plated onto the adhesion enhancement layer as a barrier layer. The plating solution used included: 25 g / L nickel sulfate, 10 g / L sodium hypophosphite, 3 mg / L DL-cysteine, 20 mg / L potassium iodate, 10 mg / L coumarin, 2 mg / L sodium dodecyl sulfate, 20 g / L sodium citrate, 12 g / L ammonium chloride, and 18 g / L sodium succinate. The pH value of the plating solution was 9.0.

[0119] An 800nm ​​copper layer is electroplated on the barrier layer as a conductive metal layer and then passivated to form a barrier-enhanced composite current collector.

[0120] Example 1.2

[0121] A 3 μm thick polyimide film was used as a polymer substrate, and it was ultrasonically cleaned in acetone for 5 min and then dried for later use.

[0122] The polymer substrate was immersed in a 4 mol / L sodium hydroxide solution for 3 min for modification treatment;

[0123] After cleaning, the polymer substrate was transferred to an activation solution containing palladium ions and immersed for 3 minutes, and then transferred to dimethylaminoborane for reduction.

[0124] A 180 nm thick nickel-phosphorus alloy was electrolessly plated onto the adhesion enhancement layer as a barrier layer. The plating solution used included: 25 g / L nickel sulfate, 10 g / L sodium hypophosphite, 3 mg / L DL-cysteine, 20 mg / L potassium iodate, 10 mg / L coumarin, 2 mg / L sodium dodecyl sulfate, 20 g / L sodium citrate, 12 g / L ammonium chloride, and 18 g / L sodium succinate. The pH value of the plating solution was 9.0.

[0125] An 800nm ​​copper layer is electroplated on the barrier layer as a conductive metal layer and then passivated to form a barrier-enhanced composite current collector.

[0126] Example 1.3

[0127] A 3 μm thick polyimide film was used as a polymer substrate, and it was ultrasonically cleaned in acetone for 5 min and then dried for later use.

[0128] The polymer substrate was immersed in a 4 mol / L sodium hydroxide solution for 3 min for modification treatment;

[0129] After cleaning, the polymer substrate was transferred to an activation solution containing palladium ions and immersed for 3 minutes, and then transferred to dimethylaminoborane for reduction.

[0130] A 2000 nm thick nickel-phosphorus alloy was electrolessly plated onto the adhesion enhancement layer as a barrier layer. The plating solution used included: 25 g / L nickel sulfate, 35 g / L sodium hypophosphite, 3 mg / L DL-cysteine, 20 mg / L potassium iodate, 10 mg / L coumarin, 2 mg / L sodium dodecyl sulfate, 20 g / L sodium citrate, 12 g / L ammonium chloride, and 18 g / L sodium succinate. The pH value of the plating solution was 9.

[0131] An 800nm ​​copper layer is electroplated on the barrier layer as a conductive metal layer and then passivated to form a barrier-enhanced composite current collector.

[0132] Example 2

[0133] A 3 μm thick polyimide film was used as a polymer substrate, and it was ultrasonically cleaned in acetone for 5 min and then dried for later use.

[0134] The polymer substrate was immersed in a 4 mol / L sodium hydroxide solution for 3 min for modification treatment;

[0135] After cleaning, the polymer substrate was transferred to an activation solution containing palladium ions and immersed for 3 minutes, and then transferred to dimethylaminoborane for reduction.

[0136] A 400 nm thick nickel-boron alloy was electrolessly plated onto the adhesion enhancement layer as a barrier layer. The plating solution used included: 25 g / L nickel sulfate, 10 g / L dimethylamine borane, 3 mg / L DL-cysteine, 20 mg / L potassium iodate, 10 mg / L coumarin, 2 mg / L sodium dodecyl sulfate, 20 g / L sodium citrate, 12 g / L ammonium chloride, and 18 g / L sodium succinate. The pH value of the plating solution was 9.

[0137] A 600nm copper layer is electroplated on the barrier layer as a metallic conductive layer and then passivated to form a barrier-enhanced composite current collector.

[0138] Example 3.1

[0139] A 3 μm thick polyimide film was used as a polymer substrate, and it was ultrasonically cleaned in acetone for 5 min and then dried for later use.

[0140] The polymer substrate was immersed in a 4 mol / L sodium hydroxide solution for 3 min for modification treatment;

[0141] After cleaning, the polymer substrate was transferred to an activation solution containing palladium ions and immersed for 3 minutes, and then transferred to dimethylaminoborane for reduction.

[0142] A 300 nm thick nickel-copper-phosphorus alloy was electrolessly plated onto the adhesion enhancement layer as a barrier layer. The plating solution used included: 25 g / L nickel sulfate, 2 g / L copper sulfate, 20 g / L sodium hypophosphite, 3 mg / L DL-cysteine, 20 mg / L potassium iodate, 10 mg / L coumarin, 2 mg / L sodium dodecyl sulfate, 30 g / L sodium citrate, 12 g / L ammonium chloride, and 0.15 g / L sodium fluoride. The pH value of the plating solution was 9.0.

[0143] A 700nm copper layer is electroplated on the barrier layer as a metallic conductive layer and then passivated to form a barrier-enhanced composite current collector.

[0144] Example 3.2

[0145] A 2 μm thick polyimide film was used as a polymer substrate, and it was ultrasonically cleaned in acetone for 5 min and then dried for later use.

[0146] The polymer substrate was immersed in a 4 mol / L sodium hydroxide solution for 3 min for modification treatment;

[0147] After cleaning, the polymer substrate was transferred to an activation solution containing palladium ions and immersed for 3 minutes, and then transferred to dimethylaminoborane for reduction.

[0148] An 850 nm thick nickel-copper-phosphorus alloy was electrolessly plated onto the adhesion enhancement layer as a barrier layer. The plating solution used included: 25 g / L nickel sulfate, 2 g / L copper sulfate, 20 g / L sodium hypophosphite, 3 mg / L DL-cysteine, 20 mg / L potassium iodate, 10 mg / L coumarin, 2 mg / L sodium dodecyl sulfate, 30 g / L sodium citrate, 12 g / L ammonium chloride, and 0.15 g / L sodium fluoride. The pH value of the plating solution was 9.0.

[0149] An 800nm ​​copper layer is electroplated on the barrier layer as a conductive metal layer and then passivated to form a barrier-enhanced composite current collector.

[0150] Example 4

[0151] A 1.5 μm thick polypropylene film was used as a polymer substrate, and it was ultrasonically cleaned in acetone for 5 min and then dried for later use.

[0152] A reinforcing precursor material is coated on both opposite surfaces of a polyimide film. The reinforcing precursor material includes: 70% ethyl acetate, 4% anhydrous ethanol, 20% acrylic oligomer, 5% epoxy resin, and 1% leveling agent. The reinforcing precursor material is dried and cured at 60°C, and then ultrasonically cleaned in acetone at 50°C for 5 minutes to form an adhesion reinforcement layer with a thickness of 100 nm.

[0153] After cleaning, the polymer substrate was transferred to an activation solution containing palladium ions and immersed for 3 minutes, and then transferred to dimethylaminoborane for reduction.

[0154] A 200 nm thick nickel-phosphorus alloy was electrolessly plated onto the adhesion enhancement layer as a barrier layer. The plating solution used included: 25 g / L nickel sulfate, 10 g / L sodium hypophosphite, 3 mg / L DL-cysteine, 20 mg / L potassium iodate, 10 mg / L coumarin, 2 mg / L sodium dodecyl sulfate, 20 g / L sodium citrate, 12 g / L ammonium chloride, and 18 g / L sodium succinate. The pH value of the plating solution was 9.0.

[0155] An 800nm ​​copper layer is electroplated on the barrier layer as a conductive metal layer and then passivated to form a barrier-enhanced composite current collector.

[0156] Comparative Example 1

[0157] A 3 μm thick polyimide film was used as a polymer substrate, and it was ultrasonically cleaned in acetone for 5 min and then dried for later use.

[0158] The polymer substrate was immersed in a 4 mol / L sodium hydroxide solution for 3 min for modification treatment;

[0159] After cleaning, the polymer substrate was transferred to an activation solution containing palladium ions and immersed for 3 minutes, and then transferred to dimethylaminoborane for reduction.

[0160] A 1000nm copper layer is electroplated on both sides of the polyimide film as a metal conductive layer, and then passivated to form a barrier-reinforced composite current collector.

[0161] Comparative Example 2

[0162] A 3 μm thick polyimide film was used as a polymer substrate, and it was ultrasonically cleaned in acetone for 5 min and then dried for later use.

[0163] The polymer substrate was immersed in a 4 mol / L sodium hydroxide solution for 3 min for modification treatment;

[0164] After cleaning, the polymer substrate was transferred to an activation solution containing palladium ions and immersed for 3 minutes, and then transferred to dimethylaminoborane for reduction.

[0165] A 1000 nm copper layer was sputtered onto both sides of the polyimide film as a conductive metal layer, and then passivated to form a barrier-reinforced composite current collector.

[0166] Comparative Example 3

[0167] A 3 μm thick polyimide film was used as a polymer substrate, and it was ultrasonically cleaned in acetone for 5 min and then dried for later use.

[0168] The polymer substrate was immersed in a 4 mol / L sodium hydroxide solution for 3 min for modification treatment;

[0169] After cleaning, the polymer substrate was transferred to an activation solution containing palladium ions and immersed for 3 minutes, and then transferred to dimethylaminoborane for reduction.

[0170] A 200 nm thick nickel-phosphorus alloy was electrolessly plated onto the adhesion enhancement layer as a barrier layer. The plating solution used included: 25 g / L nickel sulfate, 10 g / L sodium hypophosphite, 3 mg / L DL-cysteine, 20 mg / L potassium iodate, 2 mg / L sodium dodecyl sulfate, 20 g / L sodium citrate, 12 g / L ammonium chloride, and 18 g / L sodium succinate. The pH value of the plating solution was 9.

[0171] The barrier layer developed wrinkles and cracks, making it impossible to continue the copper plating test.

[0172] Comparative Example 4

[0173] A 1.5 μm thick polypropylene film was used as a polymer substrate, and it was ultrasonically cleaned in acetone for 5 min and then dried for later use.

[0174] The polymer substrate was immersed in a 4 mol / L sodium hydroxide solution for 3 min for modification treatment;

[0175] After cleaning, the polymer substrate was transferred to an activation solution containing palladium ions and immersed for 3 minutes, and then transferred to dimethylaminoborane for reduction.

[0176] A 200 nm thick nickel-phosphorus alloy was electrolessly plated onto the adhesion enhancement layer as a barrier layer. The plating solution used included: 25 g / L nickel sulfate, 10 g / L sodium hypophosphite, 3 mg / L DL-cysteine, 20 mg / L potassium iodate, 10 mg / L coumarin, 2 mg / L sodium dodecyl sulfate, 20 g / L sodium citrate, 12 g / L ammonium chloride, and 18 g / L sodium succinate. The pH value of the plating solution was 9.

[0177] The adhesion test between the barrier layer and the polymer substrate failed, making subsequent copper plating impossible.

[0178] Experiment 1: The sheet resistance and adhesion level of the barrier layers prepared in the above embodiments were tested. The non-metallic content of the barrier layers prepared in the above embodiments was tested by elemental analysis. The results are shown in Table 1. In this table, "sheet resistance 1" represents the sheet resistance of the barrier layer on the front side of the polymer substrate, and "sheet resistance 2" represents the sheet resistance of the barrier layer on the back side of the polymer substrate.

[0179] Experiment 2: The adhesion of the metal conductive layer in the current collectors prepared in the above embodiments and comparative examples was tested. The adhesion level was tested at the time of preparation (0h), after immersion in electrolyte at 85℃ for 72h, and after immersion in electrolyte at 85℃ for 168h.

[0180] The adhesion rating was tested and evaluated as follows: A 3cm long and 1cm wide strip of 3M 610 tape was applied to the metal conductive layer. Air bubbles were removed, the sample was held in place, and the tape was vertically peeled off within 2 seconds. The extent of metal conductive layer detachment was observed. No detachment was rated 5B, and detachment of more than 50% of the area was rated 0B. The test results of Example 1.1 and Comparative Example 1 can be seen in the schematic diagram. Figures 3-6 .

[0181] Table 1: Barrier Layer Performance Test Results

[0182]

[0183]

[0184] Table 2: Adhesion Test Results of Metal Conductive Layer

[0185] Metal conductive layer 0h adhesion rating 72h adhesion rating 168h adhesion rating Example 1.1 5B 5B 5B Example 1.2 5B 5B 0B Example 1.3 5B 5B 0B Example 2 5B 5B 5B Example 3.1 5B 5B 5B Example 3.2 5B 5B 5B Example 4 5B 5B 5B Comparative Example 1 5B 0B 0B Comparative Example 2 5B 0B 0B Comparative Example 3 — — — Comparative Example 4 0B — —

[0186] In Tables 1 and 2, “—” indicates that there are no test results.

[0187] exist Figures 3-6 In the image, the part on the left is the composite current collector after the adhesion test, and the part on the right is the tape after the adhesion test.

[0188] Reference Figure 3 and Figure 4 As shown, after immersion in electrolyte for 72 hours and 168 hours, the metal conductive layer of the barrier-reinforced composite current collector in Example 1.1 did not show significant detachment from the surface of the composite current collector, and no material adhered to the tape, thus demonstrating adhesion of a 5B rating. (Referring to...) Figure 5 and Figure 6 As shown, the barrier-reinforced composite current collector of Comparative Example 1 showed significant detachment after immersion in electrolyte for 72 hours and 168 hours, thus exhibiting only 0B adhesion.

[0189] Referring to Table 2, neither Comparative Example 1 nor Comparative Example 2 used an amorphous alloy material as a barrier layer. The adhesion grade of the metal conductive layer upon completion of preparation reached 5B, but after immersion in the electrolyte for 72 hours, the adhesion grade dropped to 0B, indicating that it was not resistant to electrolyte immersion. Examples 1.1 to 4 used different amorphous alloy materials as barrier layers. The adhesion of the metal conductive layer remained at 5B from the completion of preparation until 72 hours of immersion, indicating that using an amorphous alloy material as a barrier layer makes the current collector more resistant to electrolyte immersion.

[0190] As shown in Tables 1 and 2, the metal conductive layer of Example 1.1 maintained an adhesion rating of 5B after 168 hours of electrolyte immersion. In contrast, the barrier layer of Example 1.2, being thinner (less than 200 nm), experienced a decrease in adhesion rating to 0B after 168 hours of electrolyte immersion. The barrier layer in Example 1.3 had a high non-metallic content of 7.21%, resulting in poor conductivity. However, by increasing the thickness of the barrier layer, its sheet resistance was kept below 2Ω, thus enabling the preparation of a uniform and complete metal conductive layer that could withstand 168 hours of electrolyte immersion.

[0191] Example 4 uses a composite material of polypropylene and polyethylene terephthalate as a substrate, and combines it with the preparation of an adhesion enhancement layer, which enables the prepared barrier layer to have an adhesion rating of 5B, thereby maintaining a high and stable adhesion rating of the metal conductive layer.

[0192] In Comparative Example 3, the amorphous alloy material prepared using an ultrathin substrate exhibited wrinkling and cracking, thus failing to provide an effective barrier and being unsuitable as a barrier layer or for subsequent preparation of conductive metal layers. Comparative Example 4 used polypropylene as a substrate, but because no pre-prepared adhesion reinforcement layer was developed, the amorphous alloy material could not stably adhere to the substrate, making it difficult to function as a barrier layer. Consequently, the subsequently prepared conductive metal layer also failed to adhere stably to the substrate.

[0193] Please note that the above embodiments are for illustrative purposes only and do not imply any limitation on this application.

[0194] It should be understood that, unless otherwise expressly stated herein, there is no strict order in which the steps are executed, and these steps may be executed in other orders. Moreover, at least some of the steps may include multiple sub-steps or multiple stages, which are not necessarily completed at the same time, but may be executed at different times, and the execution order of these sub-steps or stages is not necessarily sequential, but may be executed in turn or alternately with other steps or at least some of the sub-steps or stages of other steps.

[0195] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on the differences from other embodiments. The same or similar parts between the various embodiments can be referred to each other.

[0196] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

Claims

1. A barrier-reinforced composite current collector, characterized in that, include: Polymer substrate, barrier layer and metal conductive layer; The barrier layer covers at least one surface of the polymer substrate, and the conductive metal layer is disposed on the side of the barrier layer away from the polymer substrate. The material of the barrier layer includes an amorphous alloy material; the amorphous alloy material is selected from one or more of nickel-phosphorus alloy, nickel-boron alloy, cobalt-phosphorus alloy, cobalt-boron alloy, and chromium-phosphorus alloy; in the amorphous alloy material, the mass content of non-metallic elements is 1% to 6%; the thickness of the barrier layer is 200 nm to 900 nm; and the sheet resistance of the barrier layer is ≤2 Ω / □. The plating solution used to prepare the amorphous alloy material includes: a main salt, a main salt reducing agent, a stabilizer, and a brightener. The brightener includes coumarin with a mass concentration of 8 mg / L to 12 mg / L and sodium dodecyl sulfonate with a mass concentration of 1 mg / L to 3 mg / L. The polymer substrate is made of polyimide.

2. The barrier-reinforced composite current collector according to claim 1, characterized in that, It also includes an adhesion enhancement layer disposed between the polymer substrate and the barrier layer, the adhesion enhancement layer being formed by film formation of raw materials including acrylic oligomers and epoxy resin.

3. The barrier-reinforced composite current collector according to claim 1, characterized in that, The conductive metal layer includes copper or aluminum.

4. The barrier-reinforced composite current collector according to any one of claims 1 to 3, characterized in that, The thickness of the metal conductive layer is 800nm~2000nm.

5. The barrier-reinforced composite current collector according to any one of claims 1 to 3, characterized in that, The thickness of the polymer substrate is 1μm to 4μm.

6. The method for preparing the barrier-reinforced composite current collector according to any one of claims 1 to 5, characterized in that, Includes the following steps: The amorphous alloy material is prepared on the polymer substrate by chemical plating to serve as the barrier layer; The metal conductive layer is prepared on the barrier layer.

7. The method for preparing the barrier-reinforced composite current collector according to claim 6, characterized in that, The plating solution used to prepare the amorphous alloy material includes: a main salt, a main salt reducing agent, a stabilizer, and a brightener. The main salt includes one or more of nickel, cobalt, and chromium. The main salt reducing agent contains one or more of boron and phosphorus. The main salt reducing agent is used to reduce the main salt, so that the non-metallic elements therein are co-deposited with the metallic elements in the main salt to form the amorphous alloy material.

8. The method for preparing the barrier-reinforced composite current collector according to claim 7, characterized in that, The stabilizer comprises potassium iodate at a mass concentration of 18 mg / L to 22 mg / L and DL-cysteine ​​at a mass concentration of 2 mg / L to 4 mg / L; and / or, The main salt comprises one or more of nickel sulfate, nickel sulfide, and nickel aminosulfonate, and the mass concentration of the main salt is 18 g / L to 30 g / L; and / or, The main salt reducing agent includes one or more of sodium hypophosphite and dimethylamine borane, and the mass concentration of the main salt reducing agent is 5 g / L to 30 g / L.

9. The method for preparing the barrier-reinforced composite current collector according to claim 8, characterized in that, The plating solution further includes a complexing agent selected from one or more of sodium citrate, aminoacetic acid, succinic acid, ethylenediaminetetraacetic acid, and lactic acid, wherein the mass concentration of the complexing agent is 15 g / L to 30 g / L; and / or The plating solution further includes an accelerator selected from one or more of malonic acid, succinic acid, glutaric acid, adipic acid, and glycine, wherein the mass concentration of the accelerator is 16 g / L to 20 g / L; and / or The pH value of the plating solution is 8.5~9.

5.

10. An electrode, characterized in that, It includes a current collector and an electrode active material disposed on the current collector, wherein the current collector is a barrier-reinforced composite current collector according to any one of claims 1 to 5.

11. A battery, characterized in that, It includes a positive electrode, a negative electrode, and an electrolyte, wherein the positive electrode and the negative electrode are disposed opposite to each other, and the electrolyte is disposed between the positive electrode and the negative electrode, and one or both of the positive electrode and the negative electrode are electrodes according to claim 10.

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