CN105154914B - A kind of preparation method of carbon fiber composite anode materials - Google Patents

Abstract

A method for preparing a carbon fiber composite anode material, comprising making a carbon fiber composite resin matrix (1) and a conductive copper beam (2) into an anode material, then pretreating the surface of the carbon fiber composite resin matrix, and then electrodepositing on the surface of the carbon fiber composite resin matrix The lead or lead alloy intermediate metal layer, and finally the active layer is electrodeposited on the surface of the carbon fiber composite resin matrix. The invention can effectively solve the problem that the carbon anode material is easily consumed when used as an anode, improve the oxidation and corrosion resistance of the carbon fiber composite resin material in the electrolysis process, prolong its service life, and effectively increase the electrocatalytic activity of the carbon fiber anode material.

Description

A kind of preparation method of carbon fiber composite anode material

technical field

The invention belongs to the technical field of composite electrode materials, in particular to a preparation method of carbon fiber composite anode materials.

Background technique

Carbon fiber has a high carbon content ratio, good electrical conductivity (resistivity of carbon fiber body is 1.2×10 ^-3 Ω·cm), and large specific surface area. It is a good electrochemical reactor. Carbon fiber composite resin materials not only have good electrical conductivity, but also have excellent mechanical properties. Carbon fiber composite resin materials have good corrosion resistance, especially in high chloride ion environments. However, since carbon fiber is a microcrystalline graphite material, it is easy to consume when it is used as an anode. Therefore, when using carbon fiber composite resin material as an anode material, carbon fiber is used as a conductive phase, and resin is used as a bonding phase. For example, in the process of electrowinning zinc, there are a large amount of SO ₄ ^2- and a small amount of ClO ^- in the electrolyte, and these ions will discharge on the anode to generate oxygen, which will lead to the consumption of CO and CO ₂ in the carbon fiber anode during the electrolysis process ( 2O ^2- (coordination)－4e+C→CO ₂ , under normal anode current density, CO ₂ is the primary product of the anode, and can generate CO under low current density).

Contents of the invention

The purpose of the present invention is to solve the existing problems of using carbon fiber composite resin materials as anode materials, provide a method that can effectively solve the problem that carbon anode materials are easily consumed when used as anodes, and improve the oxidation and corrosion resistance of carbon fiber composite resin materials in the electrolysis process A method for preparing a carbon fiber composite anode material that can effectively increase the electrocatalytic activity of the carbon fiber anode material and prolong its service life.

In order to realize the foregoing invention object, the technical scheme that the present invention takes is as follows:

A method for preparing a carbon fiber composite anode material, comprising the steps of:

(a) Make the anode material: punch the carbon fiber composite resin matrix and the conductive copper beam respectively, and pass through the holes on the carbon fiber composite resin matrix and the conductive copper beam with copper rivets, fix the carbon fiber composite resin matrix on the conductive copper beam, and then Lead is poured into the conductive copper beam to form a lead-clad copper conductive beam, and the bottom of the carbon fiber composite resin matrix is fixed with an insulating fixed base;

(b) Pretreatment of the surface of the carbon fiber composite resin matrix: put the carbon fiber composite resin matrix part of the anode material produced in step (a) into the composite alkaline degreasing solution of NaOH and Na ₂ CO ₃ for 30-60 minutes, and after degreasing Finally, wash with deionized water for 1 to 3 times, and then carry out surface pretreatment of the carbon fiber composite resin matrix with liquid phase corrosion oxidation and anodic oxidation, after the treatment is completed, wash with deionized water for 1 to 3 times; The liquid phase corrosion oxidation method is to oxidize the carbon fiber composite resin matrix in an aqueous solution with a temperature of 20-60 °C and a mass percent concentration of 5% to 20% HNO ₃ for 5-30 minutes; the anodic oxidation method refers to the carbon fiber composite resin matrix Put it in an electrolytic cell as an anode, and use graphite as a cathode for oxidation. The electrolyte in the electrolytic cell is an aqueous solution of NH ₄ HCO ₃ with a mass percentage of 5% to 10%. The current density of electrolysis is 10 to 80A/m ² . The temperature is 20～40℃, and the oxidation time is 2～10min;

(c) Electrodeposition of lead or lead alloy intermediate metal layer on the surface of the carbon fiber composite resin matrix: the carbon fiber composite resin matrix after step (b) pretreatment is placed in the lead or lead alloy composite electroplating solution as the cathode, and the pure lead plate is the anode, DC electroplating, so that a layer of lead or lead alloy intermediate metal layer is electrodeposited on the surface of the carbon fiber composite resin matrix;

(d) Electrodeposition active layer on the surface of the lead or lead alloy intermediate metal layer: the carbon fiber composite resin matrix obtained by step (c) on the surface of which the lead or lead alloy intermediate metal layer has been electrodeposited is cleaned with deionized water and used as an anode Place in the electroplating solution of the composite active layer, use stainless steel as the cathode, and direct current electroplating, so that an active layer with microhardness is electrodeposited on the lead or lead alloy intermediate layer on the surface of the carbon fiber composite resin matrix.

The carbon fiber composite resin matrix in step (a) is a plate-shaped or rod-shaped carbon fiber-reinforced resin material, the thickness of the plate-shaped carbon fiber composite resin matrix is 3-8mm, and the diameter of the rod-shaped carbon fiber composite resin matrix is 10-30mm.

The carbon fiber reinforced resin material is one or more of carbon fiber reinforced epoxy resin, carbon fiber reinforced vinyl resin, and carbon fiber reinforced unsaturated polyester resin. One or more of graphite, conductive polyaniline and graphene are added to the carbon fiber reinforced resin material.

The mass concentration range of the NaOH and Na ₂ CO ₃ composite alkaline oil removal solution in step (b) is 60-100 g/L NaOH and 15-30 g/L Na ₂ CO ₃ .

The lead or lead alloy composite electroplating solution in step (c) is a mixture of 150-200mL/L lead methanesulfonate and 0.5g/L gelatin, or 0.2-1g/L150-200mL/L lead methanesulfonate and The mixed solution of silver methanesulfonate and 0.5g/L gelatin, the electroplating process conditions are that the carbon fiber composite resin matrix is used as the cathode, the pure lead plate is used as the anode, the electroplating current density is 1~10A/m ² , and the plating time is 1~ 12h, the temperature is 20-40°C, the lead or lead alloy intermediate metal layer electrodeposited on the surface of the carbon fiber composite resin matrix is lead or lead-silver alloy, and the thickness is 20-60 μm.

The electroplating solution for the composite active layer in step (d) is a β-PbO ₂ electroplating solution, and the components of the electroplating solution are 50-200g/LPb(NO ₃ ) ₂ , 0-0.5mol/LNaF and 5-10g/L initial HNO ₃ ; The DC electroplating process conditions are to use the carbon fiber composite resin matrix as the anode, stainless steel as the cathode, the temperature of the plating solution is 40-90°C, the anode current density is 30-70mA/cm ² , and the electrodeposition time is 1-3h; on the surface of the carbon fiber composite resin matrix The microhardness active layer electrodeposited on the lead or lead alloy intermediate metal layer is a β-PbO2 active layer with a thickness of _2-3 mm and a microhardness ≥ 400Hv.

The carbon fiber composite anode material obtained by the invention effectively solves the problem that the carbon anode material is easily consumed when used as an anode, improves the service life, and effectively increases the electrocatalytic activity of the carbon fiber anode material. The carbon fiber composite anode material obtained by the method of the invention not only has good electrical conductivity, but also has excellent mechanical properties, has good corrosion resistance in a high chloride ion environment, and can effectively reduce energy consumption when used as an anode.

Description of drawings

Fig. 1 is a schematic structural view of the carbon fiber composite anode material of the present invention.

detailed description

Example 1

A method for preparing a carbon fiber composite anode material, comprising the steps of:

(a) Make the anode material: punch holes in the plate-shaped carbon fiber composite resin matrix 1 and the conductive copper beam 2 with a thickness of 8 mm, and use copper rivets 5 to pass through the holes on the carbon fiber composite resin matrix and the conductive copper beam, and insert the carbon fiber composite resin The matrix is fixed on the conductive copper beam, and then the conductive copper beam is poured with lead to form the lead-clad copper conductive beam 3, and the bottom of the carbon fiber composite resin matrix is fixed with an insulating fixed base 4. The carbon fiber reinforced resin material is carbon fiber reinforced epoxy resin. Graphite and conductive polyaniline are added to the carbon fiber reinforced resin material.

Carbon fiber composited with different resins can make carbon fiber composite anode materials applicable to various solution systems. By adding inorganic or organic conductive powder to the resin, not only the conductivity of the carbon fiber composite anode material can be improved, but also the electrochemical activity of the matrix can be improved. Therefore, the carbon fiber composite resin matrix has high mechanical strength and excellent electrical conductivity, light weight and strong plate design.

(b) Pretreatment of the surface of the carbon fiber composite resin matrix: the carbon fiber composite resin matrix part of the anode material made in step (a) is put into NaOH with a mass concentration of 80g/L and Na ₂ CO with a mass concentration of 20g/ _L The composite alkali Degreasing in the degreasing liquid for 60 minutes, cleaning with deionized water for 3 times, and then carrying out surface pretreatment on the carbon fiber composite resin matrix by liquid phase corrosion oxidation method, the process condition is an aqueous solution with a mass percentage concentration of 10% _HNO3 Medium oxidation for 5 minutes, the temperature was controlled at 40°C, and after the treatment was completed, it was washed with deionized water for 3 times.

The carbon fiber composite resin matrix has a smooth and hydrophobic surface with a lot of oil residues. In the subsequent process of electrodepositing an active surface layer on the surface of the carbon fiber composite resin matrix, the van der Waals force and mechanical fit between the coating and the substrate are weak. If the carbon fiber composite Improper pretreatment of the surface of the resin matrix will make the active surface layer uneven, the bonding force is not good, and it is easy to peel off. The destruction of the active surface layer will not only reduce the electrocatalytic activity of the electrode material, but also expose the carbon fiber composite resin matrix, accelerate its corrosion consumption process, and reduce the service life of the anode.

(c) Electrodeposition of lead or lead alloy intermediate metal layer on the surface of the carbon fiber composite resin matrix: the carbon fiber composite resin matrix after the pretreatment of step (b) is placed in the composite electroplating solution as the cathode, and the pure lead plate is used as the anode, and direct current electroplating, so that The surface of the carbon fiber composite resin matrix is electrodeposited with a lead intermediate metal layer; the composite electroplating solution is a mixed solution of 200mL/L lead methanesulfonate and 0.5g/L gelatin, and the electroplating process conditions are that the carbon fiber composite resin matrix is used as the cathode, The pure lead plate is used as the anode, the current density of electroplating is 2A/m ² , the plating time is 3h, and the temperature is 40°C to obtain a lead intermediate metal layer with a thickness of 25μm.

Electrodepositing a certain thickness of lead or lead alloy intermediate metal layer on the surface of the carbon fiber composite resin matrix can not only improve the conductivity of the carbon fiber composite anode material and the surface resistance to solution ion erosion and corrosion, but also improve the electrodeposition activity of the carbon fiber composite resin matrix and the surface. Surface bonding.

(d) Electrodeposition active layer on the surface of the lead or lead alloy intermediate metal layer: After the lead or lead alloy electrodeposition in step (c) is completed, clean the carbon fiber composite resin matrix with deionization, and place it as an anode in the composite active layer. In the first-layer electroplating solution, stainless steel is used as the cathode, and direct-current electroplating is used to electrodeposit a layer of microhardness β _- PbO2 active layer on the surface of the carbon fiber composite resin matrix. The composite active layer electroplating solution is β-PbO ₂ electroplating solution, the electroplating solution composition is 200g/L Pb(NO ₃ ) ₂ , 0.5mol/LNaF and 5g/L initial HNO ₃ ; The substrate is used as the anode, the stainless steel is used as the cathode, the bath temperature is 40°C, the anode current density is 30mA/cm ² , and the electrodeposition time is 2h; the obtained surface β-PbO ₂ active layer has a thickness of 2mm and a microhardness of 600Hv. The β-PbO ₂ active layer has anti-oxidation and corrosion resistance (higher stability in strong acid H ₂ SO ₄ or HNO ₃ ), high oxygen overpotential, good conductivity, strong binding force, and oxidation in aqueous solution. Strong ability, can pass high current and so on. Due to the uneven deposition of β-PbO ₂ on the active layer and the electrode surface and the poor mechanical properties of β-PbO ₂ itself, the deposition thickness must be controlled to ensure the combination of the active layer and the electrode surface.

Example 2

A method for preparing a carbon fiber composite anode material, comprising the steps of:

(a) Making anode materials: punch holes in the rod-shaped carbon fiber composite resin matrix and conductive copper beams with a diameter of 20 mm, and fix the carbon fiber composite resin matrix on the conductive copper beams with copper rivets, and then pour lead into the conductive copper beams to form a lead package Copper conductive beam, the bottom of the carbon fiber composite resin matrix is fixed with an insulating fixed base. The carbon fiber reinforced resin material is carbon fiber reinforced vinyl resin and carbon fiber reinforced unsaturated polyester resin. Graphene is added to the carbon fiber reinforced resin material.

(b) Pretreatment of the surface of the carbon fiber composite resin matrix: the carbon fiber composite resin matrix of the anode material made in step (a) is put into NaOH with a mass concentration of 60g/L and Na ₂ CO with a mass concentration of 30g/ _L The compound alkaline Degreasing in the degreasing liquid for 40 minutes, cleaning twice with deionized water, and then performing surface pretreatment on the carbon fiber composite resin matrix by anodic oxidation, specifically placing the carbon fiber composite resin matrix in an electrolytic cell as an anode, using graphite As the cathode for oxidation, the electrolyte in the electrolytic cell is 5% by mass NH ₄ HCO ₃ aqueous solution, the electrolytic current density is 10A/m ² , the temperature of the electrolyte is 20°C, and the oxidation time is 10 minutes. Then wash twice with deionized water.

(c) Electrodeposition of lead or lead alloy intermediate metal layer on the surface of the carbon fiber composite resin matrix: the carbon fiber composite resin matrix after the pretreatment of step (b) is placed in the composite electroplating solution as the cathode, and the pure lead plate is used as the anode, and direct current electroplating, so that A lead-silver alloy intermediate metal layer with a certain thickness is electrodeposited on the surface of the carbon fiber composite resin matrix; the composite electroplating solution is a mixed solution of 150mL/L lead methanesulfonate, 0.2g/L silver methanesulfonate and 0.5g/L gelatin , the electroplating process conditions are as follows: the carbon fiber composite resin matrix is used as the cathode, the pure lead plate is used as the anode, the current density of the electroplating is 10A/m ² , the plating time is 1h, and the temperature is 30°C to obtain a lead-silver alloy intermediate metal layer with a thickness of 54μm .

(d) Electrodeposition active layer on the surface of the lead or lead alloy intermediate metal layer: After the lead or lead alloy electrodeposition in step (c) is completed, clean the carbon fiber composite resin matrix with deionization, and place it as an anode in the composite active layer. In the first-layer electroplating solution, stainless steel is used as the cathode, and direct-current electroplating is used to electrodeposit a layer of microhardness β _- PbO2 active layer on the surface of the carbon fiber composite resin matrix. The electroplating solution for the composite active layer is β-PbO ₂ electroplating solution, and the components of the electroplating solution are 100g/L Pb(NO ₃ ) ₂ , 0.2mol/L NaF and 10g/L initial HNO ₃ ; the DC electroplating process condition is to combine carbon fibers The resin matrix is used as the anode, the stainless steel is used as the cathode, the bath temperature is 60°C, the anode current density is 40mA/cm ² , and the electrodeposition time is 3h; the obtained surface β-PbO ₂ active layer has a thickness of 2.5mm and a microhardness of 400Hv.

Example 3

A method for preparing a carbon fiber composite anode material, comprising the steps of:

(a) Making anode materials: punch holes in the rod-shaped carbon fiber composite resin matrix and conductive copper beam with a diameter of 30 mm, and fix the carbon fiber composite resin matrix on the conductive copper beam with copper rivets, and then pour lead into the conductive copper beam to form a lead package Copper conductive beam, the bottom of the carbon fiber composite resin matrix is fixed with an insulating fixed base. The carbon fiber reinforced resin material is carbon fiber reinforced vinyl resin. Graphite is added to the carbon fiber reinforced resin material.

(b) Pretreatment of the surface of the carbon fiber composite resin matrix: put the carbon fiber composite resin matrix of the anode material made in step (a) into NaOH with a mass concentration of 100g/L and Na ₂ CO with a mass concentration of 15g/ _L Composite alkaline The degreasing liquid was degreased for 30 minutes, washed with deionized water once, and then the carbon fiber composite resin matrix was subjected to surface pretreatment by anodic oxidation method, specifically, the carbon fiber composite resin matrix was placed in an electrolytic cell as an anode, As the cathode for oxidation, the electrolyte in the electrolytic cell is 10% by mass NH ₄ HCO ₃ aqueous solution, the electrolytic current density is 80A/m ² , the temperature of the electrolyte is 30°C, and the oxidation time is 6 minutes. Then wash twice with deionized water.

(c) Electrodeposition of lead or lead alloy intermediate metal layer on the surface of the carbon fiber composite resin matrix: the carbon fiber composite resin matrix after the pretreatment of step (b) is placed in the composite electroplating solution as the cathode, and the pure lead plate is used as the anode, and direct current electroplating, so that The carbon fiber composite resin matrix surface electrodeposits a lead intermediate metal layer with a certain thickness; The process conditions are as follows: the carbon fiber composite resin matrix is used as the cathode, the pure lead plate is used as the anode, the current density of electroplating is 9A/m ² , the plating time is 12h, and the temperature is 35°C to obtain a lead intermediate metal layer with a thickness of 60μm.

(d) Electrodeposition active layer on the surface of the lead or lead alloy intermediate metal layer: After the lead or lead alloy electrodeposition in step (c) is completed, clean the carbon fiber composite resin matrix with deionization, and place it as an anode in the composite active layer. In the first-layer electroplating solution, stainless steel is used as the cathode, and direct-current electroplating is used to electrodeposit a layer of microhardness β _- PbO2 active layer on the surface of the carbon fiber composite resin matrix. The composite active layer electroplating solution is β-PbO ₂ electroplating solution, the electroplating solution composition is 180g/L Pb(NO ₃ ) ₂ , 0.4mol/LNaF and 8g/L initial HNO ₃ ; the DC electroplating process condition is carbon fiber composite resin The substrate is used as the anode, the stainless steel is used as the cathode, the bath temperature is 90°C, the anode current density is 70mA/cm ² , and the electrodeposition time is 1h; the obtained surface β-PbO ₂ active layer has a thickness of 3mm and a microhardness of 400Hv.

Example 4

A method for preparing a carbon fiber composite anode material, comprising the steps of:

(a) Making anode materials: punch holes in the rod-shaped carbon fiber composite resin matrix and conductive copper beam with a diameter of 10 mm, and fix the carbon fiber composite resin matrix on the conductive copper beam with copper rivets, and then pour lead into the conductive copper beam to form a lead package Copper conductive beam, the bottom of the carbon fiber composite resin matrix is fixed with an insulating fixed base. The reinforced resin material is carbon fiber reinforced epoxy resin. Conductive polyaniline is added to the carbon fiber reinforced resin material.

(b) Pretreatment of the surface of the carbon fiber composite resin matrix: the carbon fiber composite resin matrix of the anode material made in step (a) is put into NaOH with a mass concentration of 100g/L and Na ₂ CO with a mass concentration of 25g/ _L Composite alkaline Degreasing in the degreasing liquid for 50 minutes, cleaning twice with deionized water, and then carrying out surface pretreatment on the carbon fiber composite resin matrix by liquid phase corrosion oxidation method, the process condition is in an aqueous solution with a mass percentage concentration of 20% HNO ₃ Oxidize for 10 minutes, and the temperature is controlled at 20°C. After the treatment is completed, wash it once with deionized water.

(c) Electrodeposition of lead or lead alloy intermediate metal layer on the surface of the carbon fiber composite resin matrix: the carbon fiber composite resin matrix after the pretreatment of step (b) is placed in the composite electroplating solution as the cathode, and the pure lead plate is used as the anode, and direct current electroplating, so that A lead intermediate metal layer of a certain thickness is electrodeposited on the surface of the carbon fiber composite resin matrix; the composite electroplating solution is a mixed solution of 180mL/L lead methanesulfonate, 1g/L silver methanesulfonate and 0.5g/L gelatin, and the electroplating process The conditions are that the carbon fiber composite resin matrix is used as the cathode, the pure lead plate is used as the anode, the current density of electroplating is 1A/m ² , the plating time is 10h, and the temperature is 20°C to obtain a lead intermediate metal layer with a thickness of 20μm.

(d) Electrodeposition active layer on the surface of the lead or lead alloy intermediate metal layer: After the lead or lead alloy electrodeposition in step (c) is completed, clean the carbon fiber composite resin matrix with deionization, and place it as an anode in the composite active layer. In the first-layer electroplating solution, stainless steel is used as the cathode, and direct-current electroplating is used to electrodeposit a layer of microhardness β _- PbO2 active layer on the surface of the carbon fiber composite resin matrix. The composite active layer electroplating solution is β-PbO ₂ electroplating solution, and the electroplating solution composition is 50g/L Pb(NO ₃ ) ₂ and 8g/L initial HNO ₃ ; DC electroplating process condition is that carbon fiber composite resin matrix is used as anode, stainless steel As the cathode, the bath temperature is 80°C, the anode current density is 50mA/cm ² , and the electrodeposition time is 2h; the obtained surface β-PbO ₂ active layer has a thickness of 3mm and a microhardness of 500Hv.

Example 5

A method for preparing a carbon fiber composite anode material, comprising the steps of:

(a) Making anode materials: select a plate-shaped carbon fiber composite resin matrix and conductive copper beams with a thickness of 3-6mm, punch holes respectively, and fix the carbon fiber composite resin matrix on the conductive copper beams with copper rivets, and then pour the conductive copper beams The lead forms a lead-clad copper conductive beam, and the bottom of the carbon fiber composite resin matrix is fixed with an insulating fixed base.

(b) Pretreatment of the surface of the carbon fiber composite resin matrix: the carbon fiber composite resin matrix of the anode material made in step (a) is put into NaOH with a mass concentration of 70g/L and Na ₂ CO with a mass concentration of 20g/ _L Composite alkaline Degreasing in the degreasing liquid for 40 minutes, cleaning with deionized water for 3 times, and then carrying out surface pretreatment on the carbon fiber composite resin matrix by liquid phase corrosion oxidation method, the process condition is in an aqueous solution with a mass percentage concentration of 5% HNO ₃ Oxidize for 30 minutes, the temperature is controlled at 60°C, after the treatment is completed, wash once with deionized water.

(c) Electrodeposition of lead or lead alloy intermediate metal layer on the surface of the carbon fiber composite resin matrix: the carbon fiber composite resin matrix after the pretreatment of step (b) is placed in the composite electroplating solution as the cathode, and the pure lead plate is used as the anode, and direct current electroplating; composite The electroplating solution is a mixture of 180mL/L lead methanesulfonate and 0.5g/L gelatin. The electroplating process conditions are that the carbon fiber composite resin matrix is used as the cathode, and the pure lead plate is used as the anode. The current density of the electroplating is 5A/m ² . The time is 8 hours, the temperature is 35° C., and a lead intermediate metal layer with a thickness of 25 μm is obtained.

(d) Electrodeposition active layer on the surface of the lead or lead alloy intermediate metal layer: After the lead or lead alloy electrodeposition in step (c) is completed, clean the carbon fiber composite resin matrix with deionization, and place it as an anode in the composite active layer. In the first-layer electroplating solution, stainless steel is used as the cathode, and direct-current electroplating is used to electrodeposit a layer of microhardness β _- PbO2 active layer on the surface of the carbon fiber composite resin matrix. The electroplating solution for the composite active layer is β-PbO ₂ electroplating solution, and the components of the electroplating solution are 80g/LPb(NO ₃ ) ₂ , 0.1mol/LNaF and 8g/L initial HNO ₃ ; the DC electroplating process condition is that the carbon fiber composite resin matrix As the anode, stainless steel as the cathode, the bath temperature is 80°C, the anode current density is 40mA/cm ² , and the electrodeposition time is 2h; the obtained surface β-PbO ₂ active layer has a thickness of 2.5mm and a microhardness of 600Hv.

Example 6

A method for preparing a carbon fiber composite anode material, comprising the steps of:

(a) Making the anode material: punch holes in the plate-like carbon fiber composite resin matrix and conductive copper beams with a thickness of 5 mm, and fix the carbon fiber composite resin matrix on the conductive copper beams with copper rivets, and then pour lead into the conductive copper beams to form lead Copper-clad conductive beams, the bottom of the carbon fiber composite resin matrix is fixed with an insulating fixed base.

(b) Pretreatment of the surface of the carbon fiber composite resin matrix: the carbon fiber composite resin matrix of the anode material made in step (a) is put into NaOH with a mass concentration of 60g/L and Na ₂ CO with a mass concentration of 30g/ _L The compound alkaline The degreasing liquid was degreased for 40 minutes, washed with deionized water for 3 times, and then the carbon fiber composite resin matrix was subjected to surface pretreatment by anodic oxidation, specifically, the carbon fiber composite resin matrix was placed in an electrolytic cell as an anode, and graphite As a cathode for oxidation, the electrolyte in the electrolytic cell is 8 mass percent NH ₄ HCO ₃ aqueous solution, the electrolytic current density is 50A/m ² , the temperature of the electrolyte is 40°C, and the oxidation time is 2 minutes. Then wash 3 times with deionized water.

(c) Electrodeposition of lead or lead alloy intermediate metal layer on the surface of the carbon fiber composite resin matrix: the carbon fiber composite resin matrix after the pretreatment of step (b) is placed in the composite electroplating solution as the cathode, and the pure lead plate is used as the anode, and direct current electroplating, so that A lead-silver alloy intermediate metal layer with a certain thickness is electrodeposited on the surface of the carbon fiber composite resin matrix; the composite electroplating solution is a mixed solution of 150mL/L lead methanesulfonate, 0.5g/L silver methanesulfonate and 0.5g/L gelatin , the electroplating process conditions are as follows: the carbon fiber composite resin matrix is used as the cathode, the pure lead plate is used as the anode, the electroplating current density is 8A/m ² , the plating time is 6h, and the temperature is 30°C to obtain a lead-silver alloy intermediate metal layer with a thickness of 55μm .

(d) Electrodeposition active layer on the surface of the lead or lead alloy intermediate metal layer: After the lead or lead alloy electrodeposition in step (c) is completed, clean the carbon fiber composite resin matrix with deionization, and place it as an anode in the composite active layer. In the first-layer electroplating solution, stainless steel is used as the cathode, and direct-current electroplating is used to electrodeposit a layer of microhardness β _- PbO2 active layer on the surface of the carbon fiber composite resin matrix. The composite active layer electroplating solution is β-PbO ₂ electroplating solution, the electroplating solution composition is 120g/L Pb(NO ₃ ) ₂ , 0.2mol/LNaF and 5g/L initial HNO ₃ ; the DC electroplating process condition is carbon fiber composite resin The substrate is used as the anode, the stainless steel is used as the cathode, the bath temperature is 50°C, the anode current density is 40mA/cm ² , and the electrodeposition time is 2h; the obtained surface β-PbO ₂ active layer has a thickness of 2.8mm and a microhardness of 400Hv.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the invention should be included in the protection scope of the present invention within.

The method of the invention can be widely used in the fields of electroplating, smelting, waste water treatment, cathode anticorrosion and the like.

Claims (7)

1. a preparation method of carbon fiber composite anode material, is characterized in that, method step is as follows: (a) Make the anode material: punch the carbon fiber composite resin matrix (1) and the conductive copper beam (2) respectively, and use copper rivets (5) to pass through the holes on the carbon fiber composite resin matrix and the conductive copper beam, and the carbon fiber composite resin The matrix is fixed on the conductive copper beam, and then the conductive copper beam is poured with lead to form a lead-clad copper conductive beam (3), and the bottom of the carbon fiber composite resin matrix is fixed with an insulating fixing base (4); (b) Pretreatment of the surface of the carbon fiber composite resin matrix: put the carbon fiber composite resin matrix part of the anode material produced in step (a) into the composite alkaline degreasing solution of NaOH and Na ₂ CO ₃ for 30-60 minutes, and after degreasing Finally, wash with deionized water for 1 to 3 times, and then carry out surface pretreatment of the carbon fiber composite resin matrix with liquid phase corrosion oxidation and anodic oxidation, after the treatment is completed, wash with deionized water for 1 to 3 times; The liquid phase corrosion oxidation method is to oxidize the carbon fiber composite resin matrix in an aqueous solution with a temperature of 20-60 °C and a mass percent concentration of 5% to 20% HNO ₃ for 5-30 minutes; the anodic oxidation method refers to the carbon fiber composite resin matrix Put it in an electrolytic cell as an anode, and use graphite as a cathode for oxidation. The electrolyte in the electrolytic cell is an aqueous solution of NH ₄ HCO ₃ with a mass percentage of 5% to 10%. The current density of electrolysis is 10 to 80A/m ² . The temperature is 20～40℃, and the oxidation time is 2～10min; (c) Electrodeposition of lead or lead alloy intermediate metal layer on the surface of the carbon fiber composite resin matrix: the carbon fiber composite resin matrix after step (b) pretreatment is placed in the lead or lead alloy composite electroplating solution as the cathode, and the pure lead plate is the anode, DC electroplating, so that a layer of lead or lead alloy intermediate metal layer is electrodeposited on the surface of the carbon fiber composite resin matrix; (d) Electrodeposition active layer on the surface of the lead or lead alloy intermediate metal layer: the carbon fiber composite resin matrix obtained by step (c) on the surface of which the lead or lead alloy intermediate metal layer has been electrodeposited is cleaned with deionized water and used as an anode Place in the electroplating solution of the composite active layer, use stainless steel as the cathode, and direct current electroplating, so that an active layer with microhardness is electrodeposited on the lead or lead alloy intermediate layer on the surface of the carbon fiber composite resin matrix. 2. the preparation method of a kind of carbon fiber composite anode material according to claim 1, is characterized in that, the carbon fiber composite resin matrix in the step (a) of the present invention is the resin material that the carbon fiber of plate shape or rod shape strengthens, plate shape The thickness of the carbon fiber composite resin matrix is 3-8mm, and the diameter of the rod-shaped carbon fiber composite resin matrix is 10-30mm. 3. the preparation method of a kind of carbon fiber composite anode material according to claim 2 is characterized in that, the resin material that described carbon fiber reinforces is carbon fiber reinforced epoxy resin, carbon fiber reinforced vinyl resin, carbon fiber reinforced unsaturated polyester resin one or more of them. 4. The preparation method of a kind of carbon fiber composite anode material according to claim 2 or 3, is characterized in that, one or more of graphite, conductive polyaniline, graphene are added in the resin material of described carbon fiber reinforcement kind. 5. the preparation method of a kind of carbon fiber composite anode material according to claim 1, is characterized in that, the mass concentration range of the composite alkaline degreasing liquid of _NaOH and _Na2CO3 described in step (b) is 60～100g /L NaOH and 15~30g/L Na ₂ CO ₃ . 6. The preparation method of a kind of carbon fiber composite anode material according to claim 1, characterized in that, the lead or lead alloy composite electroplating solution described in step (c) is 150～200mL/L lead methanesulfonate and 0.5g /L gelatin mixture, or 0.2～1g/L150～200mL/L lead methanesulfonate and silver methanesulfonate and 0.5g/L gelatin mixture, the electroplating process conditions are that the carbon fiber composite resin matrix is used as the cathode, The pure lead plate is the anode, the current density of electroplating is 1-10A/m ² , the plating time is 1-12h, the temperature is 20-40℃, and the lead or lead alloy intermediate metal layer electrodeposited on the surface of the carbon fiber composite resin matrix is lead Or lead-silver alloy with a thickness of 20-60 μm. 7. the preparation method of a kind of carbon fiber composite anode material according to claim 1, is characterized in that, the electroplating solution of composite active layer described in step (d) is β-PbO ₂ electroplating solution, and electroplating solution composition is 50～200g/ L Pb(NO ₃ ) ₂ , 0~0.5mol/LNaF and 5~10g/L initial HNO ₃ ; the DC electroplating process conditions are that the carbon fiber composite resin matrix is used as the anode, the stainless steel is used as the cathode, the bath temperature is 40~90℃, The anode current density is 30-70mA/cm ² , and the electrodeposition time is 1-3h; the active layer with microhardness electrodeposited on the lead or lead alloy intermediate metal layer on the surface of the carbon fiber composite resin matrix is the β-PbO ₂ active layer, which Thickness 2 ~ 3mm, microhardness ≥ 400HV.