CN105297073A - Preparation method of copper-based titanium black electrode plate - Google Patents

Abstract

The invention discloses a method for preparing a copper-based titanium oxide electrode plate, which belongs to the technical field of electrode material preparation. The copper-based titanium oxide electrode plate of the present invention includes a copper metal plate carrier and a titanium oxide film, the main components of the titanium oxide film are Ti ₄ O ₇ and TiO ₂ , wherein the content of Ti ₄ O ₇ is not less than that of titanium oxide 50% of the total mass of the film. The preparation of the copper-based titanium suboxide electrode plate of the present invention adopts plasma spraying technology, and the titanium suboxide is combined with the copper plate at high temperature to prepare the titanium suboxide thin film. The copper-based titanium suboxide electrode plate prepared by the present invention has the characteristics of low oxygen evolution potential, good conductivity, strong corrosion resistance, high mechanical strength and low cost, and can be used as a positive electrode grid for high-energy lead-acid batteries, bipolar Battery plates and other related electrochemical plates.

Description

A kind of preparation method of copper base titanium oxide electrode plate

technical field

The invention relates to a method for preparing a copper-based titanium suboxide electrode plate, and relates to the technical field of electrode material preparation.

Background technique

Titanium electrodes are stable in size, good in corrosion resistance, light in weight and high in strength, and have been rapidly and successfully used in the chlor-alkali industry. layer raw materials, not only the cost is expensive, but also the coating is easy to fall off and fail during the sulfuric acid electrolysis process. As a widely used anode material in industry, lead electrode is stable in operation in sulfuric acid system, and the surface oxide can recover by itself even if it is damaged. However, lead alloy electrodes have large internal resistance, easy to dissolve, heavy weight, low strength, and have been bent and deformed. And other fatal flaws. In order to make up for the shortage of titanium electrodes and lead electrodes, copper electrode materials with low density, low cost, high conductivity, low anode potential and good machinability are used. At the same time, in order to ensure the stability of the surface of the copper plate, it is necessary to prepare a special conductive protective layer on its surface. This protective layer needs to have high conductivity and acid corrosion resistance.

Ti ₄ O ₇ belongs to the Magneli phase titanium oxide material, which has good electrical conductivity at room temperature, and titanium oxide (Ti ₄ O ₇ ) itself is an excellent active material; Ti ₄ O ₇ has excellent electrical conductivity, High acid and alkali corrosion resistance and corrosion resistance, low oxygen evolution potential, long life, not easy to dissolve, as an electrode material, it has good catalytic activity and compatibility with catalysts. Ti ₄ O ₇ is superior to graphite and titanium metals without passivation or corrosion under high current density and high acid conditions. It has been used as electrodes for electrodeposited zinc, metal recovery, electrolytic manganese oxide, metal foil production and printed circuit board etching Liquid recycling and reuse.

The purpose of the present invention is to overcome the deficiency of large internal resistance of titanium and lead electrode plates, and provide a highly conductive, corrosion-resistant copper-based titanium suboxide electrode plate, which can be used as an electrolytic electrode plate Plates in electrochemical processes such as zinc, metal recovery, electrolytic manganese oxide, etc.

Contents of the invention

The purpose of this method is to provide a copper-based titanium oxide electrode plate, the copper-based titanium oxide electrode plate is composed of a copper metal plate carrier and a titanium oxide film on the surface of the copper metal plate, the main component of the titanium oxide film is The content of Ti ₄ O ₇ , TiO ₂ , and Ti ₄ O ₇ is not less than 50% of the total mass of the titanium oxide film.

Preferably, the thickness of the titanium dioxide film in the present invention is 70-150 μm.

Another object of this method is to provide a method for preparing the copper-based titanium oxide electrode plate, which specifically includes the following steps:

(1) Clean and sandblast the copper metal plate carrier;

(2) Titanium oxide film was prepared by plasma spraying method on the surface of copper-based carrier, and Ti ₄ O ₇ powder was melted and then sprayed on the surface of copper metal plate carrier to obtain highly conductive titanium oxide film.

Preferably, the particle size of the sand (quartz sand) in the sand blasting treatment in step (1) of the present invention is 100-500 μm.

Preferably, in the plasma spraying method in the step (2) of the present invention: the protective gas is argon and nitrogen, the nitrogen flow rate is 1800~2000L/h, the argon flow rate is 1800~2000/h, and the spraying power is 32~36kW. The powder potential is 12~16V, the spray distance is 10~14cm, and the spray angle is 90°.

Preferably, the particle size of the titanium dioxide powder in step (3) of the present invention is in the order of microns, and the particle size is between 1 and 100 μm.

The cleaning described in the present invention is conventional cleaning, which is cleaned with alkali, nitric acid and clear water successively.

The copper-based titanium suboxide electrode of the invention can be used as an electrode material in the fields of high-energy lead-acid battery positive grid, bipolar battery plate, hydrometallurgy and the like.

Beneficial effects of the present invention:

Compared with the prior art, the present invention uses plasma spraying to spray titanium dioxide powder onto the surface of the copper metal plate carrier. Because the internal resistance of copper is small, the electric loss in the reproduction process can be reduced, and the purpose of energy saving can be achieved; the density is higher than that of lead alloy The small size reduces the burden of handling; the price of copper is lower than that of titanium alloy and lead alloy, which can greatly reduce the cost of raw materials. The technology adopted in the present invention is relatively simple, and directly spraying on the surface of the copper metal plate carrier can obtain a titanium suboxide film that is well bonded to the copper metal plate, has high electrical conductivity, high mechanical strength and good corrosion resistance. Titanium plate can be used for electrolytic deposition of zinc, metal recycling, electrolytic manganese oxide, metal foil production and recycling of printed circuit board etching solution, and can also be used as positive grid of high-energy lead-acid battery, bipolar battery plate and others Related electrochemical plates.

Description of drawings

Figure 1 is a schematic diagram of the preparation process of copper-based titanium oxide.

Fig. 2 is the XRD spectrum of the TiO thin films prepared in Examples 1(a), 2(b) and 3(c).

Fig. 3 is the SEM image of the titanium oxide thin film prepared in embodiment 1 (a), 2 (b), 3 (c).

detailed description

The present invention will be described in further detail below in conjunction with the accompanying drawings and specific embodiments, but the protection scope of the present invention is not limited to the content described.

Example 1

(1) Clean the electrolytic copper plate, soak the copper plate with lye (1mol/L) for 20 minutes to remove oil, then use 10% HNO ₃ solution for room temperature ultrasonic cleaning for 5 minutes, take it out and wash it with water and soak it in absolute ethanol solution; After drying, perform sandblasting treatment (the particle size of the quartz sand is 500 μm) to obtain a copper substrate 1 with a roughened surface.

(2) Preparation of TiO thin film on roughened copper substrate by plasma spraying method 2: Fix the roughened copper substrate on the working frame, put Ti ₄ O ₇ powder with a particle size range of 20-50 μm Into the powder feeder, set the nitrogen flow rate to 2000L/h, the argon flow rate to 2000L/h, the spraying power to 36kW, the powder feeding potential to 16V, and the spraying distance to 10cm. After the powder is uniform and continuous, click the pre-programmed spraying path on the computer to spray, and use the good bonding force between titanium dioxide and copper to obtain a copper-based titanium dioxide electrode plate with high conductivity and good mechanical properties.

(3) Perform phase characterization of the sprayed titanium dioxide film. From the XRD pattern of the film in Figure 2(a), it can be seen that the analysis is based on the diffraction peaks of TiO ₂ and Ti ₄ O ₇ , and the composition of the film is quantitatively analyzed. It can be seen that the content of Ti ₄ O ₇ is 61.5%, and the content of TiO ₂ is relatively close to that of Ti ₄ O ₇ ; from the SEM analysis of Figure 3(a), it can be seen that the thickness of the titanium oxide film is 110 μm, and it is dense, copper-based It is well combined with the titanium oxide film; therefore, the invention can prepare a copper-based titanium oxide film with high conductivity and strong mechanical properties.

Example 2

(1) Clean the electrolytic copper plate, soak the copper plate with lye (1mol/L) for 20 minutes to remove oil, then use 10% HNO ₃ solution for room temperature ultrasonic cleaning for 5 minutes, take it out and wash it with water and soak it in absolute ethanol solution; After drying, perform sandblasting treatment (the particle size of the quartz sand is 300 μm), to obtain a copper substrate 1 with a roughened surface.

(2) Preparation of TiO thin film on roughened copper substrate by plasma spraying method 2: Fix the roughened copper substrate on the working frame, put Ti ₄ O ₇ powder with a particle size range of 40-70 μm Into the powder feeder, set the nitrogen flow rate to 1900L/h, the argon flow rate to 1900L/h, the spraying power to 32kW, the powder feeding potential to 14V, and the spraying distance to 14cm. After the powder is uniform and continuous, click the pre-programmed spraying path on the computer to spray, and use the good bonding force between titanium dioxide and copper to obtain a copper-based titanium dioxide electrode plate with high conductivity and good mechanical properties.

(3) Perform phase characterization of the sprayed titanium oxide film. From the XRD pattern of the film in Figure 2(b), it can be seen that the analysis is based on the diffraction peaks of TiO ₂ and Ti ₄ O ₇ , and the composition of the film is quantitatively analyzed. It can be seen that the content of Ti ₄ O ₇ is 69.3%, and the content of Ti ₄ O ₇ is relatively high; from the SEM analysis of Figure 3(b), it can be seen that the thickness of the titanium suboxide film is 80 μm, and it is dense, and the copper-based and titanium suboxide films The combination is good; therefore, the invention can be used to prepare a copper-based titanium oxide film with high conductivity and strong mechanical properties.

Example 3

(1) Clean the electrolytic copper plate, soak the copper plate with lye (1mol/L) for 20 minutes to remove oil, then use 10% HNO ₃ solution for room temperature ultrasonic cleaning for 5 minutes, take it out and wash it with water and soak it in absolute ethanol solution; After drying, sandblasting is performed (the particle size of the quartz sand is 100 μm) to obtain a copper substrate 1 with a roughened surface.

(2) Preparation of TiO thin film on roughened copper substrate by plasma spraying method 2: Fix the roughened copper substrate on the working frame, put Ti ₄ O ₇ powder with a particle size range of 60-90 μm Into the powder feeder, set the nitrogen flow rate to 1800L/h, the argon flow rate to 1800L/h, the spraying power to 34kW, the powder feeding potential to 15V, and the spraying distance to 12cm. After the powder is uniform and continuous, click the pre-programmed spraying path on the computer to spray, and use the good bonding force between titanium dioxide and copper to obtain a copper-based titanium dioxide electrode plate with high conductivity and good mechanical properties.

(3) Perform phase characterization of the sprayed titanium dioxide film. From the XRD pattern of the film in Figure 2(c), it can be seen that the analysis is based on the diffraction peaks of TiO ₂ and Ti ₄ O ₇ , and the composition of the film is quantitatively analyzed. It can be seen that the content of Ti ₄ O ₇ is 73.4%, and the content of Ti ₄ O ₇ is relatively high; from the SEM analysis of Figure 3(c), it can be seen that the thickness of the titanium suboxide film is 130 μm, and it is dense, copper-based and titanium suboxide film The combination is good; therefore, the invention can be used to prepare a copper-based titanium oxide film with high conductivity and strong mechanical properties.

Claims (6)

1. the sub-Titanium oxide electrode plate of copper base, is characterized in that: the sub-Titanium oxide electrode plate of described copper base is by copper metal sheet carrier and the sub-thin film of titanium oxide being in copper metal sheet surface, and the main component of sub-thin film of titanium oxide is Ti ₄o ₇, TiO ₂, Ti ₄o ₇content is not less than 50% of sub-thin film of titanium oxide total mass.

2. the sub-Titanium oxide electrode plate of copper base according to claim 1, is characterized in that: the film thickness of described sub-titanium oxide is 70 ~ 150 μm.

3. the preparation method of the sub-Titanium oxide electrode plate of copper base described in claim 1 or 2, is characterized in that, specifically comprise the following steps:

(1) copper metal sheet carrier is cleaned, sandblasting;

(2) plasma spraying method is adopted to prepare sub-thin film of titanium oxide, by Ti on copper base carrier surface ₄o ₇sub-thin film of titanium oxide copper metal sheet carrier surface obtaining high conductivity is sprayed to after powder smelting.

4. the preparation method of the sub-Titanium oxide electrode plate of copper base according to claim 3, is characterized in that: the granularity of the described sandblasting medium sand of step (1) is 100 ~ 500 μm.

5. the preparation method of the sub-Titanium oxide electrode plate of copper base according to claim 3; it is characterized in that: in step (2) in plasma spraying method: protection gas is argon gas and nitrogen; nitrogen flow rate is 1800 ~ 2000L/h; argon gas flow velocity is 1800 ~ 2000L/h; spray power is 32 ~ 36kW; powder feeding current potential is 12 ~ 16V, and spray distance is 10 ~ 14cm, and jet angle is 90 °.

6. the preparation method of the sub-Titanium oxide electrode plate of copper base according to claim 3, is characterized in that: Ti described in step (2) ₄o ₇the granularity of powder is 1 ~ 100 μm.