Graphene copper mixed electrolyte, graphene metal composite material and conductor

Abstract

The invention relates to the technical field of negative electrode materials, in particular to a graphene copper mixed electrolyte, a graphene metal composite material and a conductor. The graphene and copper mixed electrolyte comprises graphene, copper salt, acid, a displacement agent and a dispersing agent, the displacement agent comprises at least one of polyether and sulfydryl imidazoline, and the concentration of the displacement agent is 5-20 mg / L. According to the graphene and copper mixed electrolyte system provided by the invention, copper ions and graphene can be deposited more compactly and flatly, the content and spacing of graphene are controlled within a certain range, and the purpose of improving the tensile strength of the copper foil is achieved; the graphene metal composite material provided by the invention has relatively high tensile strength; a conductor prepared by adopting the graphene metal composite material provided by the invention not only has relatively good conductivity, but also has relatively high tensile strength, and can effectively cope with thinner application scenes with relatively large tensile force.

Description

Technical Field

[0001] This application relates to the field of negative electrode material technology, specifically to a graphene-copper mixed electrolyte, a graphene-metal composite material, and a conductor. Background Technology

[0002] The negative electrode of a lithium-ion battery typically consists of a negative current collector and a negative active material. The negative current collector serves as a carrier for coating the negative active material and is used to collect and transport the negative electron flow. It is generally made of conductive materials such as copper foil. With the development of lithium-ion battery technology, higher energy density is required, necessitating thinner negative electrode sheets. To avoid affecting electrochemical performance, the negative current collector is typically made thinner, requiring thinner copper foil. However, thinner copper foil reduces its tensile strength and other properties. During processes such as coating the negative active material and winding the bare cell, the copper foil needs to be stretched, making it prone to breakage. The reduced tensile strength and other properties of the copper foil further decrease the stability of the battery manufacturing process.

[0003] Graphene possesses excellent mechanical and electrical properties. In related technologies, it is hoped that adding graphene to metallic conductor materials to form graphene-metal composites can improve the performance of the conductors. For example, adding graphene to copper foil can improve its tensile strength, while the addition of graphene, with its good electrical conductivity, is unlikely to adversely affect the conductivity of the copper foil. However, when graphene is mixed with copper for electroplating, the improvement effect is not significant. Summary of the Invention

[0004] This application aims to provide a graphene-copper hybrid electrolyte, a graphene-metal composite material, and a conductor to improve the mechanical properties of copper foil.

[0005] The embodiments of this application are implemented as follows:

[0006] In a first aspect, embodiments of this application provide a graphene-copper mixed electrolyte, comprising graphene, copper salt, acid, a leveling agent, and a dispersant, wherein the leveling agent comprises at least one of polyether and mercaptoimidazoline, and the concentration of the leveling agent is 5-20 mg / L.

[0007] In one embodiment of this application, the dispersant comprises sodium lignosulfonate; and / or

[0008] The concentration of the dispersant is 10-30 g / L.

[0009] In one embodiment of this application, the copper salt includes at least one of copper sulfate, copper phosphate, and copper pyrophosphate; and / or

[0010] The acid includes at least one of sulfuric acid, copper sulfate, and pyrophosphate; and / or

[0011] The concentration of the copper salt is 200-400 g / L; and / or

[0012] The concentration of the acid is 80-120 g / L.

[0013] In one embodiment of this application, the concentration of graphene is 0.1-5 g / L.

[0014] In one embodiment of this application, the electrolyte further includes a brightener, wherein:

[0015] The brightening agent includes at least one of sodium phenyl dithiopropane sulfonate and sodium dithiopropane sulfonate; and / or

[0016] The concentration of the brightener is 1-10 mg / L.

[0017] In one embodiment of this application, the electrolyte further includes a wetting agent, wherein:

[0018] The wetting agent includes at least one of sodium diethylpropane sulfonate, sodium dodecyl sulfonate, and sodium dodecyl sulfate; and / or

[0019] The concentration of the wetting agent is 0.1-1 mg / L.

[0020] In one embodiment of this application, the electrolyte further includes a conductive salt, wherein:

[0021] The conductive salt includes sodium chloride; and / or

[0022] The concentration of the conductive salt is 15-95 mg / L.

[0023] Secondly, embodiments of this application provide a graphene-metal composite material, comprising:

[0024] Conductive substrate;

[0025] A graphene-copper hybrid layer is disposed on at least one surface of the conductive substrate, wherein the graphene-copper hybrid layer is formed using the electrolyte described in any one of the first aspects.

[0026] In one embodiment of this application, the thickness of the graphene-copper hybrid layer is 0.5-10 μm; and / or

[0027] The graphene-copper hybrid layer contains 1.5-5% carbon, of which 98-99.5% is graphene; and / or

[0028] In the thickness direction of the graphene-copper hybrid layer, the spacing between adjacent graphene particles is 0.6-0.9 μm; and / or

[0029] In the direction perpendicular to the thickness direction of the graphene-copper hybrid layer, the spacing between adjacent graphene particles is 0.1-0.4 μm.

[0030] Thirdly, embodiments of this application provide a conductor comprising the graphene-metal composite material described in any one of the second aspects, wherein the conductor is a wire, cable, electrical contact, battery connector, or negative electrode current collector.

[0031] Beneficial effects:

[0032] The technical solution provided in this application, by configuring a specific leveling agent in a graphene-copper mixed electrolyte system and further controlling the concentration of the leveling agent at 5-20 mg / L, ensures uniform graphene distribution and consistent deposition posture. This results in a high graphene content that is less prone to agglomeration into carbon, with a graphene spacing of 0.6-0.9 μm in the deposition thickness direction and a spacing of 0.1-0.4 μm on the same deposition surface. Furthermore, the carbon content in the graphene-copper mixed layer is 1.5-5%, and the graphene content within the carbon content is 98-99.5%. This leads to a more uniform distribution of copper ions and graphene, resulting in a denser and smoother deposition, better utilization of graphene properties, and ultimately, improved tensile strength of the copper foil.

[0033] The graphene-metal composite material prepared using the electrolyte provided in this application has graphene embedded in copper metal in a relatively uniform manner, with a uniform and orderly distribution. There is an appropriate spacing between adjacent graphene particles, and the carbon content in the graphene-copper hybrid layer and the graphene content in the carbon content are controlled within an appropriate range, so that the graphene-metal composite material has high tensile strength.

[0034] Conductors made from the graphene-metal composite materials provided in this application, such as wires, cables, electrical contacts, battery connectors, or negative electrode current collectors, not only have good conductivity but also high tensile strength, which can effectively cope with thinner applications and applications with greater tensile force. Attached Figure Description

[0035] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0036] Figure 1 This is a schematic diagram of the graphene-copper composite material provided in the embodiments of this application.

[0037] Icons: 100 - Conductive substrate; 200 - Graphene-copper hybrid layer; 210 - Graphene; X - First direction; Y - Second direction; Z - Third direction. Detailed Implementation

[0038] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. Furthermore, it should be understood that the specific embodiments described herein are only for illustration and explanation of this application and are not intended to limit this application.

[0039] In this application, unless otherwise stated, directional terms such as "upper" and "lower" generally refer to the upper and lower positions of the device in its actual use or operating state, specifically the drawing directions in the accompanying drawings; while "inner" and "outer" refer to the outline of the device. Furthermore, in the description of this application, the term "comprising" means "including but not limited to". The terms first, second, third, etc., are used merely as illustrative purposes and do not impose numerical requirements or establish a numerical order.

[0040] In this application, "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural.

[0041] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one," "at least one of the following," or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c," or "at least one of a, b, and c," can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0042] Various embodiments of this application may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a hard limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is referred to herein, it means including any referenced number (fraction or integer) within the referred range.

[0043] Copper foil is usually manufactured by two methods: electrolytic preparation and rolling preparation. Electrolytic copper foil has higher purity and controllable thickness, which is beneficial for producing thinner copper foil as the raw material for negative electrode current collectors. However, the copper foil produced in this way has poor tensile strength.

[0044] To improve the tensile strength and other mechanical properties of copper foil, graphene is added to form a composite material, with the aim of improving the tensile properties of copper foil without affecting its conductivity. However, the improvement effect is not significant.

[0045] Based on this, this application provides a technical solution, which involves configuring a graphene-copper mixed electrolyte, adding a dispersant and a specific type and concentration of a leveling agent—5-20 mg / L of polyether and / or mercaptoimidazoline—to make the copper ion deposition more uniform and dense. Furthermore, graphene can co-deposit with copper ions, filling the deposition pores of the copper ions and making the deposition even denser. This process produces a double-sided photoelectrolytic copper foil with uniformly distributed graphene. On one hand, the high density of the copper foil itself improves its tensile strength; on the other hand, the graphene uniformly distributed in the copper can fully exert its enhancing effect, achieving the goal of effectively improving the tensile strength of the copper foil.

[0046] In a first aspect, embodiments of this application provide a graphene-copper mixed electrolyte, the electrolyte comprising graphene, copper salt, acid, a leveling agent and a dispersant, the leveling agent comprising at least one of polyether and mercaptoimidazoline, the concentration of the leveling agent being 5-20 mg / L.

[0047] In this electrolyte system, under the combined action of the dispersant and mercaptoimidazoline and / or polyether, graphene is uniformly dispersed in the electrolyte and can be deposited along with copper ions. Specifically, this electrolyte system allows for a higher deposition rate of copper ions at concave points than at convex points, thus preventing excessive copper ion deposition at convex points and filling concave points with more deposited copper ions. This results in a more uniform copper ion distribution and a denser copper foil, thereby improving tensile strength. Simultaneously, during deposition, the high-molecular-weight dispersant encapsulates the graphene to form micelles carrying the same charge. Due to steric hindrance and the repulsive force between like charges, the particles cannot agglomerate and disperse. The graphene is deposited at a certain spacing, filling the pores where copper ions are deposited, resulting in a denser deposition. This mitigates the adverse effects of uneven graphene distribution and agglomeration in existing technologies, further improving the tensile strength of the copper foil. Therefore, the electrolyte system provided in this application embodiment can make copper ions and graphene more evenly distributed, deposited more densely and smoothly, thereby achieving the purpose of improving the tensile strength of copper foil.

[0048] Furthermore, in this electrolyte system, the factor affecting the different deposition rates of copper ions at concave and convex points lies in the fact that different potentials on the cathode surface (positive terminal of the differential capacitor) form films of varying thicknesses under the action of mercaptoimidazoline and polyether. The film is thicker at the convex locations, slowing down the release rate of copper complex ions, while the film is thinner at the concave locations, essentially having no impact on the deposition rate of copper ions. This application further controls the concentration of the leveling agent to ensure that the deposition rates of copper ions and graphene are within a suitable ratio range, thereby controlling the spacing and deposition posture of the deposited graphene, resulting in uniform graphene distribution, roughly consistent deposition posture, high graphene content, and resistance to carbon agglomeration. For example, in this electrolyte system, the concentration of the leveling agent is configured to be 5 mg / L, 6 mg / L, 7 mg / L, 8 mg / L, 9 mg / L, 10 mg / L, 11 mg / L, 13 mg / L, 15 mg / L, 16 mg / L, 18 mg / L, 19 mg / L, or 20 mg / L, so that the spacing of graphene in the deposition thickness direction is 0.6-0.9 μm, the spacing on the same deposition surface is 0.1-0.4 μm, and the carbon content in the graphene-copper hybrid layer is 1.5-5%, with the graphene content in the carbon content being 98-99.5%, thereby better utilizing the performance of graphene and achieving the purpose of improving tensile strength.

[0049] Simultaneously, due to the effect of the film layer, the number of new nucleation sites in the crystal increases without concentrating and enlarging at the protrusions, resulting in smaller and more compact crystal formation. This increases the surface area of ​​contact between crystals (i.e., the number of metallic bonds formed), strengthens the bonding force, and further improves the tensile strength. Furthermore, the reduction half-wave potentials of these two substances are equal to or similar to those of hydrated copper ions, which also contributes to a certain brightening effect.

[0050] In some embodiments, the dispersant includes sodium lignosulfonate.

[0051] Sodium lignosulfonate is a large organic molecule with its hydrophilic end pointing towards the electrolyte solution. After dissolving in the solution, the hydrophilic end carries a large number of negative charges, while the hydrophobic end is adsorbed onto graphene sheets and combines with graphene. This encapsulates the graphene within micelles formed by sodium lignosulfonate. Because the hydrophilic ends of the micelles carry negative charges, they repel each other due to their similar charges, resulting in uniform dispersion of graphene in the electrolyte. At the same time, the micelles formed by sodium lignosulfonate also have steric hindrance, preventing particle contact and aggregation. During electroplating, graphene co-deposits with copper ions or fills the pores of copper ion deposition, making the deposition more dense and thus improving the tensile strength of the copper foil.

[0052] In some embodiments, the concentration of the dispersant is 10-30 g / L. For example, the concentration of the dispersant is 10 g / L, 11 g / L, 13 g / L, 15 g / L, 16 g / L, 18 g / L, 20 g / L, 21 g / L, 22 g / L, 24 g / L, 26 g / L, 27 g / L, 28 g / L, 29 g / L, or 30 g / L.

[0053] In some embodiments, the copper salt includes at least one of copper sulfate, copper phosphate, and copper pyrophosphate.

[0054] In some embodiments, the acid includes at least one of sulfuric acid, copper sulfate, and pyrophosphate.

[0055] In some embodiments, the concentration of the copper salt is 200-400 g / L. For example, the concentration of the copper salt is 200 g / L, 220 g / L, 225 g / L, 230 g / L, 240 g / L, 250 g / L, 260 g / L, 265 g / L, 280 g / L, 290 g / L, 300 g / L, 310 g / L, 315 g / L, 320 g / L, 325 g / L, 330 g / L, 335 g / L, 340 g / L, 345 g / L, 350 g / L, 355 g / L, 360 g / L, 365 g / L, 370 g / L, 375 g / L, 380 g / L, 385 g / L, 390 g / L, 395 g / L, or 400 g / L.

[0056] In some embodiments, the concentration of the acid is 80-120 g / L. For example, the concentration of the acid is 80 g / L, 83 g / L, 85 g / L, 88 g / L, 90 g / L, 92 g / L, 95 g / L, 98 g / L, 100 g / L, 105 g / L, 110 g / L, 112 g / L, 115 g / L, 118 g / L, or 120 g / L.

[0057] In some embodiments, the concentration of graphene is 0.1-5 g / L. For example, the concentration of graphene is 0.1 g / L, 0.2 g / L, 0.5 g / L, 0.7 g / L, 0.8 g / L, 1.0 g / L, 1.2 g / L, 1.5 g / L, 1.7 g / L, 1.9 g / L, 2.0 g / L, 2.3 g / L, 2.5 g / L, 2.6 g / L, 2.8 g / L, 3.0 g / L, 3.1 g / L, 3.4 g / L, 3.5 g / L, 3.7 g / L, 3.9 g / L, 4.0 g / L, 4.2 g / L, 4.5 g / L, 4.8 g / L, 4.9 g / L, or 5.0 g / L.

[0058] In some embodiments, the electrolyte further includes a brightener, wherein the brightener includes at least one of sodium phenyl dithiopropane sulfonate and sodium dithiopropane sulfonate.

[0059] Sodium phenyl dithiopropane sulfonate and sodium dithiopropane sulfonate are added as brighteners to the electrolyte system. The brighteners are adsorbed by the leveling agents mercaptoimidazoline and / or polyether. Under the synergistic effect of the brighteners, leveling agents, dispersants, etc., a better brightening effect is achieved.

[0060] Take sodium phenyl dithiopropane sulfonate as an example. On one hand, during the reaction, the disulfide bonds in sodium phenyl dithiopropane sulfonate break, and the sulfonate ions carry a negative charge. They are adsorbed at the positive terminal of the differential capacitor in the electric double layer. When adsorption and desorption reach dynamic equilibrium, a portion of the sulfonate ions remain at the positive terminal of the differential capacitor, serving as a transit carrier for hydrated copper ions to enter the cathode surface. On the other hand, copper ions exist in solution as hydrated copper ions, with spatial structures including octahedral and planar quadrilateral structures. With the help of the carrier (sulfonate ions), they reach the cathode surface more quickly, accelerating the process and preparing for the next electrochemical reaction. The reaction is prepared in advance; on the other hand, the complexation constant of disulfide bonds with copper ions is greater than that of hydroxyl bonds with copper ions, causing disulfide bonds to break on the cathode surface, followed by the complexation of copper ions to form a stronger copper ion complex, which forms a film on the cathode surface. Simultaneously, chloride ions act as a piercing and bridging agent on the cathode surface, accelerating the reduction rate of copper complex ions on the cathode surface. Furthermore, it can increase the cathode polarization (illusory), increasing the number of active sites on the cathode surface. This results in a new crystal nucleus formation rate greater than the crystal growth rate, leading to a smoother coating. Therefore, under the combined effect of these three aspects, sodium phenyl dithiopropane sulfonate acts as a carrier, increases cathode polarization and coordination, improves surface smoothness, optimizes copper foil quality, and makes the crystals denser, thereby further enhancing the tensile strength of the copper foil.

[0061] In some embodiments, the concentration of the brightener is 1-10 mg / L. For example, the concentration of the brightener is 1.0 mg / L, 1.5 mg / L, 2.0 mg / L, 2.5 mg / L, 3.0 mg / L, 3.5 mg / L, 4.0 mg / L, 4.5 mg / L, 5.0 mg / L, 5.5 mg / L, 6.0 mg / L, 6.5 mg / L, 7.0 mg / L, 7.5 mg / L, 8.0 mg / L, 8.5 mg / L, 9.0 mg / L, 9.5 mg / L, or 10 mg / L.

[0062] In some embodiments, the electrolyte further includes a wetting agent, wherein the wetting agent includes at least one of sodium diethylpropane sulfonate, sodium dodecyl sulfonate, and sodium dodecyl sulfate.

[0063] During the foil formation process on the cathode surface, the current density is high. The metallic activity of copper and hydrogen is similar, meaning their deposition potentials are similar. A large amount of active hydrogen or hydrogen gas is generated on the cathode surface. However, the cathode surface has high tension, resulting in poor adsorption of liquids but strong adsorption of active hydrogen or hydrogen gas. This active hydrogen or hydrogen gas remains on the cathode surface, forming an insulator. Consequently, no copper or graphene deposits at these sites, leading to pinholes in the copper foil and reduced density. Adding the aforementioned wetting agent effectively wets the cathode surface, reduces surface tension, prevents the retention of active hydrogen or hydrogen gas, effectively improves density, and also wets the graphene sheets, allowing for better bonding between graphene and the dispersant, improving graphene dispersibility and deposition uniformity.

[0064] In some embodiments, the concentration of the wetting agent is 0.1-1 mg / L. For example, the concentration of the wetting agent is 0.1 mg / L, 0.15 mg / L, 0.2 mg / L, 0.25 mg / L, 0.3 mg / L, 0.35 mg / L, 0.4 mg / L, 0.45 mg / L, 0.5 mg / L, 0.55 mg / L, 0.6 mg / L, 0.65 mg / L, 0.7 mg / L, 0.75 mg / L, 0.8 mg / L, 0.85 mg / L, 0.9 mg / L, 0.95 mg / L, or 1 mg / L.

[0065] In some embodiments, the electrolyte further includes a conductive salt, wherein the conductive salt includes sodium chloride.

[0066] In some embodiments, the concentration of the conductive salt is 15-95 mg / L. For example, the concentration of the conductive salt is 15 mg / L, 20 mg / L, 22 mg / L, 25 mg / L, 28 mg / L, 30 mg / L, 35 mg / L, 40 mg / L, 43 mg / L, 45 mg / L, 48 mg / L, 50 mg / L, 55 mg / L, 60 mg / L, 65 mg / L, 70 mg / L, 75 mg / L, 80 mg / L, 85 mg / L, 90 mg / L, or 95 mg / L.

[0067] Secondly, such as Figure 1 As shown, this application provides a graphene-metal composite material, which includes a conductive substrate 100 and a graphene-copper hybrid layer 200. The conductive substrate 100 is made of a conductive material, such as copper or graphite. The graphene-copper hybrid layer 200 is disposed on at least one surface of the conductive substrate 100, and the graphene-copper hybrid layer 200 is formed using the electrolyte provided in the first aspect.

[0068] The conductive substrate 100 can be sheet-like, linear, rod-like, or irregularly shaped. Taking a sheet-like conductive substrate 100 as an example, please further consider... Figure 1 The conductive substrate 100 extends along a first direction X and has two opposing side surfaces along a second direction Y. The first direction X and the second direction Y are perpendicular to each other. The graphene-copper hybrid layer 200 covers at least one side surface of the conductive substrate 100. Therefore, the graphene-copper hybrid layer 200 also extends along the first direction X and has a thickness along the second direction Y and a width along the third direction Z.

[0069] In some embodiments, the thickness of the graphene-copper hybrid layer 200 is 0.5-10 μm.

[0070] In some embodiments, the carbon content in the graphene-copper hybrid layer 200 is 1.5-5%, and the graphene content in the carbon content is 98-99.5%.

[0071] In some embodiments, the spacing between adjacent graphene 210s in the thickness direction of the graphene-copper hybrid layer 200 is 0.6-0.9 μm. The thickness direction of the graphene-copper hybrid layer 200 is along the second direction Y, that is, the spacing between adjacent graphene 210s in the second direction Y is 0.6-0.9 μm.

[0072] In some embodiments, the spacing between adjacent graphene 210 is 0.1-0.4 μm in a direction perpendicular to the thickness direction of the graphene-copper hybrid layer 200. That is, in the plane containing the first direction X and the third direction Z, the spacing between adjacent graphene is 0.1-0.4 μm.

[0073] The electrolyte provided in the first aspect of the embodiments of this application, under the synergistic effect and mutual competition of each component, not only enables the copper ions to be deposited more smoothly and densely, but also enables the graphene sheets to be mostly embedded in the deposited copper in an attitude perpendicular to the second direction Y. That is, the graphene sheets are deposited in an attitude parallel to the surface of the conductive substrate 100, and an appropriate spacing is formed between adjacent graphene sheets, so that the graphene is uniformly and orderly distributed. At the same time, the carbon content in the graphene-copper hybrid layer and the graphene content in the carbon content are controlled within a suitable range, so that the formed graphene-copper hybrid layer has high tensile strength.

[0074] Thirdly, embodiments of this application provide a conductor comprising the graphene-metal composite material provided in the second aspect. This conductor can be used in any device that requires electrical conductivity and / or thermal conductivity, for example, the conductor is a wire, cable, electrical contact, battery connector, or negative electrode current collector.

[0075] The battery connector includes at least one of the following electrical connectors: battery busbar, positive and negative terminals or positive and negative terminals of the battery, and adapter between the battery tab and the terminal.

[0076] The conductors made from the graphene-metal composite materials provided in this application not only have good electrical conductivity but also high tensile strength, effectively addressing applications requiring thinner materials and greater tensile forces. For example, when using the graphene-metal composite materials provided in this application to prepare negative electrode current collectors, even with a thinner thickness, they exhibit good tensile strength. During processes requiring tension, such as coating active materials and winding bare cells, breakage is less likely to occur, improving production process stability and increasing the yield rate of battery products, which is beneficial for the development of high-energy-density batteries.

[0077] The present application will be specifically described below through specific embodiments. The following embodiments are only some embodiments of the present application and are not intended to limit the present application.

[0078] Example 1

[0079] S1, Prepare the electrolyte. The electrolyte consists of 2.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 6 mg / L sodium phenyl dithiopropane sulfonate, 0.5 mg / L sodium diethylpropane sulfonate, 8 mg / L polyether, 3 mg / L mercaptoimidazoline, and 10 g / L sodium lignin sulfonate.

[0080] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0081] Example 2

[0082] S1, Prepare the electrolyte. The electrolyte consists of 2.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 6 mg / L sodium phenyl dithiopropane sulfonate, 0.5 mg / L sodium diethylpropane sulfonate, 15 mg / L polyether, 3 mg / L mercaptoimidazoline, and 10 g / L sodium lignin sulfonate.

[0083] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0084] Example 3

[0085] S1, Prepare the electrolyte. The electrolyte consists of 2.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 6 mg / L sodium phenyl dithiopropane sulfonate, 0.5 mg / L sodium diethylpropane sulfonate, 2 mg / L polyether, 3 mg / L mercaptoimidazoline, and 10 g / L sodium lignin sulfonate.

[0086] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0087] Example 4

[0088] S1, Prepare the electrolyte. The electrolyte consists of 2.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 6 mg / L sodium phenyl dithiopropane sulfonate, 0.5 mg / L sodium diethylpropane sulfonate, 8 mg / L polyether, 10 mg / L mercaptoimidazoline, and 10 g / L sodium lignin sulfonate.

[0089] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0090] Example 5

[0091] S1, Prepare the electrolyte. The electrolyte consists of 2.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 6 mg / L sodium phenyl dithiopropane sulfonate, 0.5 mg / L sodium diethylpropane sulfonate, 8 mg / L polyether, 1 mg / L mercaptoimidazoline, and 10 g / L sodium lignin sulfonate.

[0092] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0093] Example 6

[0094] S1, Prepare the electrolyte. The electrolyte consists of 2.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 6 mg / L sodium phenyl dithiopropane sulfonate, 0.5 mg / L sodium diethylpropane sulfonate, 8 mg / L polyether, 3 mg / L mercaptoimidazoline, and 20 g / L sodium lignin sulfonate.

[0095] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0096] Example 7

[0097] S1, Prepare the electrolyte. The electrolyte consists of 2.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 6 mg / L sodium phenyl dithiopropane sulfonate, 0.5 mg / L sodium diethylpropane sulfonate, 8 mg / L polyether, 3 mg / L mercaptoimidazoline, and 30 g / L sodium lignin sulfonate.

[0098] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0099] Example 8

[0100] S1, Prepare the electrolyte. The electrolyte consists of 2.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 9 mg / L sodium phenyl dithiopropane sulfonate, 0.5 mg / L sodium diethylpropane sulfonate, 8 mg / L polyether, 3 mg / L mercaptoimidazoline, and 10 g / L sodium lignin sulfonate.

[0101] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0102] Example 9

[0103] S1, Prepare the electrolyte. The electrolyte consists of 2.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 6 mg / L sodium dithiopropane sulfonate, 0.5 mg / L sodium diethylpropane sulfonate, 8 mg / L polyether, 3 mg / L mercaptoimidazoline, and 10 g / L sodium lignin sulfonate.

[0104] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0105] Example 10

[0106] S1, Prepare the electrolyte. The electrolyte consists of 2.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 6 mg / L sodium phenyl dithiopropane sulfonate, 0.9 mg / L sodium diethylpropane sulfonate, 8 mg / L polyether, 3 mg / L mercaptoimidazoline, and 10 g / L sodium lignin sulfonate.

[0107] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0108] Example 11

[0109] S1, Prepare the electrolyte. The electrolyte consists of 2.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 6 mg / L sodium phenyl dithiopropane sulfonate, 0.5 mg / L sodium dodecyl sulfonate, 8 mg / L polyether, 3 mg / L mercaptoimidazoline, and 10 g / L sodium lignin sulfonate.

[0110] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0111] Example 12

[0112] S1, Prepare the electrolyte. The electrolyte consists of 4.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 6 mg / L sodium phenyl dithiopropane sulfonate, 0.5 mg / L sodium diethylpropane sulfonate, 8 mg / L polyether, 3 mg / L mercaptoimidazoline, and 10 g / L sodium lignin sulfonate.

[0113] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0114] Comparative Example 1

[0115] S1, Prepare the electrolyte. The electrolyte consists of 2.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 6 mg / L sodium phenyl dithiopropane sulfonate, 0.5 mg / L sodium diethylpropane sulfonate, and 10 g / L sodium lignin sulfonate.

[0116] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0117] Comparative Example 2

[0118] S1, Prepare the electrolyte. The electrolyte consists of 2.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 6 mg / L sodium phenyl dithiopropane sulfonate, 0.5 mg / L sodium diethylpropane sulfonate, 1 mg / L polyether, 3 mg / L mercaptoimidazoline, and 10 g / L sodium lignin sulfonate.

[0119] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0120] Comparative Example 3

[0121] S1, Prepare the electrolyte. The electrolyte consists of 2.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 6 mg / L sodium phenyl dithiopropane sulfonate, 0.5 mg / L sodium diethylpropane sulfonate, 8 mg / L polyether, 15 mg / L mercaptoimidazoline, and 10 g / L sodium lignin sulfonate.

[0122] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0123] Comparative Example 4

[0124] S1, Prepare the electrolyte. The electrolyte includes 2.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 6 mg / L sodium phenyl dithiopropane sulfonate, 0.5 mg / L sodium diethylpropane sulfonate, 8 mg / L polyether, and 3 mg / L mercaptoimidazoline.

[0125] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0126] Comparative Example 5

[0127] S1, Prepare the electrolyte. The electrolyte consists of 2.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 6 mg / L sodium phenyl dithiopropane sulfonate, 0.5 mg / L sodium diethylpropane sulfonate, 8 mg / L polyether, 3 mg / L mercaptoimidazoline, and 5 g / L sodium lignin sulfonate.

[0128] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0129] Comparative Example 6

[0130] S1, Prepare the electrolyte. The electrolyte consists of 2.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 6 mg / L sodium phenyl dithiopropane sulfonate, 0.5 mg / L sodium diethylpropane sulfonate, 8 mg / L polyether, 3 mg / L mercaptoimidazoline, and 42 g / L sodium lignin sulfonate.

[0131] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0132] Comparative Example 7

[0133] S1, Prepare the electrolyte. The electrolyte consists of 2.5 g / L graphene, 300 g / L copper sulfate, 100 g / L sulfuric acid, 50 mg / L chloride ions, 6 mg / L sodium phenyl dithiopropane sulfonate, 0.5 mg / L sodium diethylpropane sulfonate, 11 mg / L polyethylene glycol, and 10 g / L sodium lignosulfonate.

[0134] S2, using the electrolyte from S1, prepares a graphene-copper hybrid layer with a thickness of 5 μm on a conductive substrate.

[0135] The graphene-metal composite materials obtained in Examples 1-12 and Comparative Examples 1-7 were tested, including using a universal tensile testing machine to test their tensile strength and testing their Zeta potential.

[0136] Table 1

[0137]

[0138] As shown in Table 1:

[0139] Compared with Comparative Examples 1-7, Examples 1-12 show that the graphene-metal composite materials prepared using the electrolyte provided in this application have significantly improved tensile properties.

[0140] Comparing Example 1 with Examples 2, 3, 4, and 5, it is shown that the electrolyte system provided in this application can achieve good results by adjusting the concentration and ratio of the leveling agent within a certain range. Comparing Example 1 with Comparative Examples 1, 2, 3, and 7, it is evident that the improvement effect is limited when the leveling agent provided in this application is not used, or when the concentration and ratio of the leveling agent exceed the concentration range provided in this application.

[0141] Comparing Example 1 with Examples 6-10, and with Comparative Examples 4, 5, and 6, it is shown that adjusting the concentration and selection of dispersant, brightener, and wetting agent within the scope provided in this application can still achieve a good improvement effect. When the scope provided in this application is exceeded, the improvement effect is limited.

[0142] Comparing Example 1 with Examples 11 and 12, it can be seen that the concentrations of graphene and copper salt in this application can be adjusted within a certain range.

[0143] As can be seen from the above, the electrolyte system provided in this application embodiment can effectively improve the mechanical properties of the graphene-copper hybrid layer under the synergistic effect and mutual competition of each component, and the resulting graphene-metal composite material has high tensile strength.

[0144] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A graphene copper hybrid electrolyte, characterized in that, The dispersant comprises sodium lignosulfonate; and / or 2. The graphene copper hybrid electrolyte of claim 1, wherein, The dispersant comprises sodium lignosulfonate; and / or The concentration of the dispersant is 10-30 g / L. 3.The graphene copper mixed electrolyte of claim 1, wherein: The copper salt comprises at least one of copper sulfate, copper phosphate, copper pyrophosphate; and / or The acid comprises at least one of sulfuric acid, copper sulfate, pyrophosphoric acid; and / or The concentration of the copper salt is 200-400 g / L; and / or The concentration of the acid is 80-120 g / L.

4. The graphene copper hybrid electrolyte of claim 1, wherein, The concentration of the graphene is 0.1-5 g / L.

5. The graphene copper hybrid electrolyte of claim 1, wherein, The electrolyte further comprises a brightener, wherein: The brightener comprises at least one of sodium phenyldithiopropyl sulfonate, sodium dithiodipropyl sulfonate; and / or The concentration of the brightener is 1-10 mg / L.

6. The graphene copper hybrid electrolyte of claim 1, wherein, The electrolyte further comprises a wetting agent, wherein: The wetting agent comprises at least one of sodium diethylpropane sulfonate, sodium dodecyl sulfonate, sodium dodecyl sulfate; and / or The concentration of the wetting agent is 0.1-1 mg / L.

7. The graphene copper hybrid electrolyte of claim 1, wherein, The electrolyte further comprises a conductive salt, wherein: The conductive salt comprises sodium chloride; and / or The concentration of the conductive salt is 15-95 mg / L.

8. A graphene metal composite, characterized by, The conductive substrate comprises: A conductive substrate; A graphene copper mixed layer is arranged on at least one side surface of the conductive substrate, and the graphene copper mixed layer is formed by the electrolyte of any one of claims 1-7.

9. The graphene metal composite of claim 8, wherein, The thickness of the graphene copper mixed layer is 0.5-10 μm; and / or The carbon content in the graphene copper mixed layer is 1.5-5%, and the graphene content in the carbon content is 98-99.5%; and / or The distance between adjacent graphenes in the thickness direction of the graphene copper mixed layer is 0.6-0.9 μm; and / or The distance between adjacent graphenes in the direction perpendicular to the thickness direction of the graphene copper mixed layer is 0.1-0.4 μm.

10. A conductor, characterized by The conductor comprises the graphene metal composite material of claim 8 or 9, and the conductor is a wire, a cable, an electrical contact, a battery connector, or a negative current collector.

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