PREPARATION METHOD OF COPPER-BASED GRAPHENE COMPOSITE WITH HIGH THERMAL CONDUCTIVITY

Abstract

A preparation method of a copper-based graphene composite with high thermal conductivity is provided. A new electrodeposited solution is used for direct current (DC) electrodeposition at a reasonable electrodeposition frequency, which fabricates a new copper-based graphene composite with high tensile strength and thermal conductivity. The copper-based graphene composite prepared by electrodeposition has high thermal conductivity of 390-1112 W/(m.Math.k) and tensile strength of 300-450 MPa, which meets the requirements in the field of thermal conduction.

Claims

1. A preparation method of a copper-based graphene composite with a high thermal conductivity, comprising the following steps: (1) preparing an electrodeposition solution for the copper-based graphene composite, wherein the electrodeposition solution comprises additives of thiourea and boric acid; (2) an activation of anode and cathode plates: washing the anode and cathode plates with an activation solution to remove oil, rust, and a surface oxide film, wherein the activation solution comprises: 50 mL of sulfuric acid and 350 mL of deionized water; and (3) conducting an electrodeposition with the electrodeposition solution prepared in step (1) to obtain the copper-based graphene composite, wherein the electrodeposition refers to a direct current (DC) electrodeposition.

2. The preparation method of the copper-based graphene composite according to claim 1, wherein the electrodeposition solution for the copper-based graphene composite in step (1) is composed of the following components in mass concentration: 90-200 g/L of copper sulfate pentahydrate, 2-20 mg/L of thiourea, 1-10 g/L of boric acid, 10-50 mg/L of polyethylene glycol (PEG) fatty acid ester, 0.05-2.0 g/L of graphene and a balance of deionized water.

3. The preparation method of the copper-based graphene composite according to claim 1, wherein a method for preparing the electrodeposition solution in step (1) comprises: subjecting a graphene solution to an ultrasonic dispersion and a dispersion in a high-speed homogenizer; mixing thiourea, boric acid, and PEG fatty acid ester into the graphene solution, accompanying with mechanical stirring; and mixing and dispersing a copper sulfate solution with the graphene solution by an electric mixer and the high-speed homogenizer to obtain the electrodeposition solution for the copper-based graphene composite.

4. The preparation method of the copper-based graphene composite according to claim 1, wherein the DC electrodeposition in step (3) is conducted under the following electrical parameters: 20-180 mA/cm.sup.2 of a current density and 300-1,000 Hz of a DC frequency; and the DC electrodeposition is conducted under the following environmental parameters: 0.5-5.0 h of an electrodeposition time, 15-50° C. of an electrodeposition solution temperature and 0.5-3 of an electrodeposition solution pH.

5. The preparation method of the copper-based graphene composite according to claim 1, wherein a coating obtained in step (3) has a thickness of 30 μm to 300 μm.

6. The copper-based graphene composite according to claim 1, wherein the copper-based graphene composite has a thermal conductivity of 390-1,112 W/(m.Math.k) and a tensile strength of 300-450 MPa.

7. A method of using the copper-based graphene composite prepared by the preparation method according to claim 1, comprising: using the copper-based graphene composite in a field of thermal conduction.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0024] FIG. 1 shows an image of a heat dissipation coating made of the copper-based graphene composite prepared in the present disclosure.

[0025] FIG. 2 shows a transmission electron microscopy (TEM) image of the copper-based graphene composite prepared in the present disclosure.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0026] The present disclosure will be described in further detail below with reference to examples. In the following examples, the preparation of 1 L of an electrodeposition solution for the copper-based graphene composite is taken as an example.

EXAMPLE 1

[0027] An electrodeposition solution for copper-based graphene was prepared according to the following component ratio: 200 g/L of copper sulfate pentahydrate, 0.05 g/L of graphene, 2 mg/L of thiourea, 2 g/L of boric acid, 10 mg/L of PEG fatty acid ester and the balance of deionized water. The anode and cathode plates were washed with an activation solution to remove oil, rust, and a surface oxide film, where the activation solution included: 50 mL of sulfuric acid and 350 mL of deionized water. The electrodeposition solution had a temperature of 20° C. and a pH of 0.5. DC electrodeposition was conducted under the following electrical parameters: 180 mA/cm.sup.2 of current density, 300 Hz of electrodeposition frequency and 0.5 h of electrodeposition time. Under the above conditions, a coating with a uniform thickness of about 30 μm, had a bright surface and average denseness. The coating of the example can reach a thermal conductivity as high as 390 W/(m.Math.k), and a tensile strength as high as 313±10 MPa.

[0028] The electrodeposition solution for the copper-based graphene composite was prepared as follows: a graphene solution with an alkyl surfactant was subjected to ultrasonic dispersion and then to dispersion in a high-speed homogenizer. Then thiourea, boric acid, and PEG fatty acid ester are mixed into the graphene, accompanying with mechanical stirring. Secondly, a copper sulfate solution is mixed and dispersed with the graphene solution by an electric mixer and a high-speed homogenizer to obtain the electrodeposition solution for the copper-based graphene composite.

EXAMPLE 2

[0029] An electrodeposition solution for copper-based graphene was prepared according to the following component ratio: 200 g/L of copper sulfate pentahydrate, 1.0 g/L of graphene, 5 mg/L of thiourea, 4 g/L of boric acid, 20 mg/L of PEG fatty acid ester and the balance of deionized water. The anode and cathode plates were washed with an activation solution to remove oil, rust, and a surface oxide film, where the activation solution included: 50 mL of sulfuric acid and 350 mL of deionized water. The electrodeposition solution had a temperature of 30° C. and a pH of 1.0. DC electrodeposition was conducted under the following electrical parameters: 180 mA/cm.sup.2 of current density, 500 Hz of electrodeposition frequency and 0.5 h of electrodeposition time. Under the above conditions, a coating with a uniform thickness of about 40 μm, had a bright surface and excellent denseness. The coating of the example can reach a thermal conductivity as high as 636 W/(m.Math.k), and a tensile strength as high as 408±10 MPa.

[0030] The electrodeposition solution was prepared by the same method as in Example 1.

EXAMPLE 3

[0031] An electrodeposition solution for copper-based graphene was prepared according to the following component ratio: 200 g/L of copper sulfate pentahydrate, 2 g/L of graphene, 10 mg/L of thiourea, 6 g/L of boric acid, 30 mg/L of PEG fatty acid ester and the balance of deionized water. The anode and cathode plates were washed with an activation solution to remove oil, rust, and a surface oxide film, where the activation solution included: 50 mL of sulfuric acid and 350 mL of deionized water. The electrodeposition solution had a temperature of 30° C. and a pH of 1.5. DC electrodeposition was conducted under the following electrical parameters: 180 mA/cm.sup.2 of current density, 500 Hz of electrodeposition frequency and 1 h of electrodeposition time. Under the above conditions, a coating with a uniform thickness of about 80 μm, had a bright surface and excellent denseness. The coating of the example can reach a thermal conductivity as high as 1,112 W/(m.Math.k), and a tensile strength as high as 450±10 MPa.

[0032] The electrodeposition solution was prepared by the same method as in Example 1.

EXAMPLE 4

[0033] An electrodeposition solution for copper-based graphene was prepared according to the following component ratio: 200 g/L of copper sulfate pentahydrate, 2 g/L of graphene, 20 mg/L of thiourea, 10 g/L of boric acid, 40 mg/L of PEG fatty acid ester and the balance of deionized water. The anode and cathode plates were washed with an activation solution to remove oil, rust, and a surface oxide film, where the activation solution included: 50 mL of sulfuric acid and 350 mL of deionized water. The electrodeposition solution had a temperature of 30° C. and a pH of 2.0. DC electrodeposition was conducted under the following electrical parameters: 180 mA/cm.sup.2 of current density, 800 Hz of electrodeposition frequency and 5 h of electrodeposition time. Under the above conditions, a coating with a uniform thickness of about 300 μm, had a small number of bulges on the surface and excellent denseness. The coating of the example can reach a thermal conductivity as high as 608 W/(m.Math.k), and a tensile strength as high as 364±10 MPa.

[0034] The electrodeposition solution was prepared by the same method as in Example 1.

EXAMPLE 5

[0035] An electrodeposition solution for copper-based graphene was prepared according to the following component ratio: 200 g/L of copper sulfate pentahydrate, 3.5 g/L of graphene, 20 mg/L of thiourea, 10 g/L of boric acid, 50 mg/L of PEG fatty acid ester and the balance of deionized water. The anode and cathode plates were washed with an activation solution to remove oil, rust, and a surface oxide film, where the activation solution included: 50 mL of sulfuric acid and 350 mL of deionized water. The electrodeposition solution had a temperature of 30° C. and a pH of 3. DC electrodeposition was conducted under the following electrical parameters: 180 mA/cm.sup.2 of current density, 1,000 Hz of electrodeposition frequency and 5 h of electrodeposition time. Under the above conditions, a coating with a uniform thickness of about 300 μm, had a large number of bulges on the surface and excellent denseness. The coating of the example can reach a thermal conductivity as high as 544 W/(m.Math.k), and a tensile strength as high as 323±10 MPa.

[0036] The electrodeposition solution was prepared by the same method as in Example 1.

COMPARATIVE EXAMPLE 1

[0037] An electrodeposition solution for copper-based graphene was prepared according to the following component ratio: 200 g/L of copper sulfate pentahydrate, 2 g/L of graphene and the balance of deionized water. The anode and cathode plates were washed with an activation solution to remove oil, rust, and a surface oxide film, where the activation solution included: 50 mL of sulfuric acid and 350 mL of deionized water. The electrodeposition solution had a temperature of 30° C. and a pH of 1.5. DC electrodeposition was conducted under the following electrical parameters: 180 mA/cm.sup.2 of current density, 500 Hz of electrodeposition frequency and 1 h of electrodeposition time. Under the above conditions, a coating with a uniform thickness of about 75 μm, had an average denseness and a smooth surface without pores. The coating of the example can reach a thermal conductivity as high as 584 W/(m.Math.k), and a tensile strength as high as 276±10 MPa.

COMPARATIVE EXAMPLE 2

[0038] An electrodeposition solution for copper-based graphene was prepared according to the following component ratio: 200 g/L of copper sulfate pentahydrate, 2 g/L of graphene, 10 mg/L of thiourea, 30 mg/L of PEG fatty acid ester and the balance of deionized water. The anode and cathode plates were washed with an activation solution to remove oil, rust, and a surface oxide film, where the activation solution included: 50 mL of sulfuric acid and 350 mL of deionized water. The electrodeposition solution had a temperature of 30° C. and a pH of 1.5. DC electrodeposition was conducted under the following electrical parameters: 180 mA/cm.sup.2 of current density, 500 Hz of electrodeposition frequency and 1 h of electrodeposition time. Under the above conditions, a coating with a uniform thickness of about 80 μm, had an average denseness and a bright surface with some bulges. The coating of the example can reach a thermal conductivity as high as 568 W/(m.Math.k), and a tensile strength as high as 342±10 MPa.

COMPARATIVE EXAMPLE 3

[0039] An electrodeposition solution for copper-based graphene was prepared according to the following component ratio: 200 g/L of copper sulfate pentahydrate, 2 g/L of graphene, 10 mg/L of thiourea, 6 g/L of boric acid, 30 mg/L of PEG fatty acid ester and the balance of deionized water. The thiourea, boric acid, and PEG fatty acid ester were subjected to dispersion with a graphene dispersion in a high-speed homogenizer, and then a resulting mixture was mixed with a copper sulfate solution. The anode and cathode plates were washed with an activation solution to remove oil, rust, and a surface oxide film, where the activation solution included: 50 mL of sulfuric acid and 350 mL of deionized water. The electrodeposition solution had a temperature of 30° C. and a pH of 1.5. DC electrodeposition was conducted under the following electrical parameters: 180 mA/cm.sup.2 of current density, 500 Hz of electrodeposition frequency and 1 h of electrodeposition time. Under the above conditions, a coating with a uniform thickness of about 260 μm, had an average denseness, a large number of bulges and a small number of pores on the surface. The coating of the example can reach a thermal conductivity as high as 696 W/(m.Math.k), and a tensile strength as high as 324±10 MPa.

[0040] The above examples are preferred implementations of the present disclosure, but the present disclosure is not limited to the above implementations. Any obvious improvement, substitution, or modification made by those skilled in the art without departing from the essence of the present disclosure should fall within the protection scope of the present disclosure.