CN112159987A - Sandwich structure composite lead electrode and preparation method thereof - Google Patents

Sandwich structure composite lead electrode and preparation method thereof Download PDF

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CN112159987A
CN112159987A CN202010917204.7A CN202010917204A CN112159987A CN 112159987 A CN112159987 A CN 112159987A CN 202010917204 A CN202010917204 A CN 202010917204A CN 112159987 A CN112159987 A CN 112159987A
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lead
foamed
layer
hot
substrate
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罗国华
顾晓聪
刘碧华
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Guangdong Zhending Environmental Technology Co ltd
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D19/00—Casting in, on, or around objects which form part of the product
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C25D17/12—Shape or form
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
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Abstract

The invention relates to the technical field of electrodes, in particular to a sandwich structure composite lead electrode and a preparation method thereof. The composite lead electrode comprises two composite layers and a support material, wherein the support material is a titanium mesh which is arranged between the two composite layers; the preparation method comprises the following preparation steps: preheating the foamed copper, hot dip plating the preheated foamed copper, forming a lead dioxide layer on the surface of the foamed lead, preheating the foamed lead substrate, and injecting lead into the preheated foamed lead substrate. The sandwich structure composite lead electrode has long service life and high stability, and because the lead dioxide layer covers the surface of the foamed lead, the compact lead dioxide layer is arranged in the three-dimensional direction of the lead anode, and a lead dioxide protective layer is easily formed in the using process, so the service life is extremely long. Moreover, the preparation method of the invention greatly reduces the manufacturing cost.

Description

Sandwich structure composite lead electrode and preparation method thereof
Technical Field
The invention relates to the technical field of electrodes, in particular to a sandwich structure composite lead electrode and a preparation method thereof.
Background
It is well known that lead metal electrodes are suitable for electrodes for electrolysis requiring corrosion resistance or high oxygen overvoltage, such as electrolysis for generating oxygen, anodic oxidation, electroplating, electrolysis of organic materials, electrolytic treatment of waste water, etc., and many improvements have been made in the electrodes. However, since there are some practical problems, there are still areas to be improved in the industrial application of these electrodes. Lead oxide used as such electrodes is of two types, i.e., orthorhombic α -PbO2And tetragonal β -PbO2 of titanium (rutile) type structure. Albeit in alpha-PbO2When used as an electrolytic anode, has corrosion resistance better than that of beta-PbO2Poor, but when alpha-PbO is produced electrolytically on a metal substrate (e.g., titanium)2Then, alpha-PbO with very small internal strain can be obtained by electroplating2. On the other hand, although beta-PbO2Has good electrical conductivity and good corrosion resistance, but if the beta-PbO is formed by an electrolytic process2Then the internal strain induced by electroplating is generally increased, thereby generating cracks or decreasing beta-PbO2Bonding properties to metal substrates.
As described above, known lead oxide-plated electrodes involve various problems due to the performance and manufacturing of lead oxide, and excellent electrodes have not been practically obtained.
As is well known, the lead electrode acts as an anode and serves three purposes, the first being as a conductor providing a current path. The second is to provide mechanical action to maintain a certain shape. Thirdly, as a medium of electrochemical reaction, water loses electrons on the surface of the anode and oxygen is separated out. In the process, due to the corrosivity of the used medium, the corrosion of the anode presents two modes, one mode is laminar shedding, namely lead is corroded, and the film layers of lead dioxide and the like on the surface layer present laminar shedding, so that the life loss is fatal influence, and the service life is greatly reduced. The second is that the surface of lead forms a lead dioxide layer which gradually dissolves slowly, and the lead anode can obtain the longest service life in the failure mode. The third failure mode is that the anode surface cannot form an effective lead dioxide film, and a continuous lead layer is electrochemically dissolved, in which case the anode has a very short life and cannot function as an insoluble anode.
How to improve the service life of the catalyst as a medium of electrochemical reaction is an object to be sought by the engineer. The composition and crystal form of the metal have great influence on the service life of the anode, and scientists have studied a lot for the anode, and the essence is that the anode is in a slow electrochemical dissolution state instead of a fast dissolution state when the anode fails to work as much as possible in the using process aiming at different using media and matching different alloy materials, and meanwhile, a place for electrode reaction is provided to separate out oxygen. I.e. is desired to be in the second state. To achieve the second state, it is critical to form a lead dioxide passivation film. In a medium containing high corrosiveness, such as chloride ions, a passive film is difficult to form, lead is easy to corrode, the first failure mode or the third failure mode is caused, and the service life is extremely short.
Meanwhile, the existing lead electrode can be dissolved in a small amount and deposited in a cathode product, but most of the lead electrode falls off and falls into an electroplating bath to form anode mud. These are not required by the user. Therefore, it is necessary to consider how to reuse these materials repeatedly, rather than treat them as waste to be disposed of in landfills, resulting in environmental pollution.
For this reason, the above-described problems are urgently needed to be solved.
Disclosure of Invention
The invention aims to provide a sandwich structure composite lead electrode with long service life and high stability and a preparation method thereof aiming at the defects of the prior art.
The invention is realized by the following technical scheme.
The composite lead electrode with the sandwich structure comprises two composite layers and a support material, wherein the support material is a titanium net which is arranged between the two composite layers.
The composite layer comprises a substrate, and the surface of the substrate sequentially comprises a hot-dip lead layer, a lead dioxide layer and a hot-melt lead layer from bottom to top.
Wherein the substrate is a copper foam, the copper foam has a thickness of 5mm, a pore size of 50-100PPI, and a unit area weight of 50 g/m.
Wherein the thickness of the hot-dip lead coating is 50-200 μm.
The preparation method of the sandwich structure composite lead electrode comprises the following preparation steps:
1) preheating: preheating the foam copper to 130-180 ℃;
2) and hot dip coating: hot dip plating the preheated foamy copper in lead or lead alloy liquid to form a hot-dip plated lead layer on the surface of the foamy copper so as to prepare foamy lead;
3) pre-forming a film: taking foamed lead as an anode and stainless steel as a cathode, and electrolyzing in a sulfuric acid medium without chloride ions to form a lead dioxide layer on the surface of the foamed lead to prepare a foamed lead substrate;
4) and then preheating: preheating a foamed lead substrate to 130-180 ℃;
5) and hot lead injection: putting the preheated foamed lead substrate into a mould, wherein the lowest layer is the foamed lead substrate with the surface fully covered with a lead dioxide layer, the middle layer is a titanium net, the upper layer is the foamed lead substrate with the surface fully covered with the lead dioxide layer, closing the mould, vacuumizing, injecting lead or lead alloy liquid, preserving heat, enabling the lead or lead alloy liquid to flow into all gaps, filling the gaps and pores, rapidly cooling, solidifying, and forming a hot melt-cast lead layer on the surface of the lead dioxide layer to obtain the sandwich structure composite lead electrode.
Wherein, the preheating in the step 1) is specifically as follows: the copper foam is preheated to 130-180 ℃ by hot air, the air temperature of the hot air is 130-180 ℃, and the air pressure is 0.10-0.15 MPa.
Wherein the hot dip coating in the step 2) specifically comprises the following steps: and (3) hot dip plating the preheated foamy copper in lead or lead alloy liquid at 350-380 ℃ for 5-10 min, blowing the plated foamy copper by using a hot air knife, wherein the temperature of the hot air is 150-180 ℃, the pressure of the hot air is 0.25-0.50 MPa, and forming a hot-dip plated lead layer on the surface of the foamy copper to obtain the foamy lead.
The step 3) of pre-filming specifically comprises the following steps: taking foamed lead as an anode and stainless steel as a cathode, electrolyzing in a sulfuric acid medium with the concentration of 5% and without chloride ions, wherein the current density of electrolysis is 0.5A/square decimeter, and the time is 4-16h, and forming a lead dioxide layer on the surface of the foamed lead to prepare the foamed lead substrate.
Wherein, the step 5) of hot lead injection specifically comprises the following steps: putting the preheated foamed lead substrate into a mould, wherein the lowest layer is the foamed lead substrate with the surface fully covered with a lead dioxide layer, the middle layer is a titanium net, the upper layer is the foamed lead substrate with the surface fully covered with the lead dioxide layer, closing the mould, vacuumizing to minus 0.1 bar, injecting lead or lead alloy liquid at 350-380 ℃, preserving the temperature for 1min, enabling the lead or lead alloy liquid to flow into all gaps, filling the gaps and the pores, then quickly cooling, solidifying, and forming a heat-formed fusion-cast lead layer on the surface of the lead dioxide layer to obtain the sandwich-structured composite lead electrode.
Wherein, the step 5) is followed by the following steps:
6) anode life test
In 150 g/l aqueous sulfuric acid at 60 ℃ with 100A/dm2Carrying out an accelerated electrolysis test on the sandwich structure composite lead electrode by using the current density;
7) chlorine ion resistance test
Adding hydrochloric acid with chloride ion of 5 g/L into 150 g/L sulfuric acid water solution, and heating at 60 deg.C with 100A/dm2And carrying out an accelerated electrolysis test on the sandwich structure composite lead electrode by using the current density.
The use of the sandwich structure composite lead electrode of the invention: in the use process of the sandwich structure composite lead electrode, because the lead dioxide layer covers the surface of the foamed lead, the compact lead dioxide layer is arranged in the three-dimensional direction of the lead anode, and a lead dioxide protective layer is easily formed in the use process, so the service life is extremely long. A small amount of the fallen micro powder is deposited at the bottom of the tank and recovered, and a small amount of the fallen micro powder is collected by a filter membrane of a filter and then recovered.
The reuse of the lead metal of the sandwich structure composite lead electrode comprises the following steps: when the sandwich structure composite lead electrode is used, the lead dioxide is gradually increased along with the consumption of the anode, the lead dioxide is dissolved in acetic acid and electroplated on the surface of polyurethane foam to prepare a metal foam lead base material, and the recycling of lead metal is realized. By the method, lead metal can be recycled, and highly toxic lead metal and compounds thereof cannot be discharged to the environment, so that great economic benefit and environmental benefit are obtained.
The invention has the beneficial effects that: the sandwich structure composite lead electrode has long service life and high stability, and the electrode is provided with a compact lead dioxide plating layer with excellent binding property on a metal substrate, wherein the lead dioxide plating layer has smaller internal strain generated by electroplating; because the lead dioxide layer covers the surface of the foamed lead, the compact lead dioxide layer is arranged in the three-dimensional direction of the lead anode, and a lead dioxide protective layer is easily formed in the using process, so that the service life is extremely long. Moreover, the preparation method of the invention greatly reduces the manufacturing cost.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1.
The preparation method of the sandwich structure composite lead electrode comprises the following preparation steps:
the foam copper with the thickness of 5mm, the pore diameter of 50PPI and the unit area weight of 50 g/square decimeter is selected.
1) Preheating: adopting hot air to preheat the foam copper to 130 ℃, wherein the air temperature of the hot air is 130 ℃, and the air pressure is 0.10 MPa;
2) and hot dip coating: hot dip plating the preheated foamy copper in lead or lead alloy liquid at 350 ℃ for 10min, blowing the plated foamy copper by a hot air knife, wherein the temperature of hot air is 150 ℃, the pressure of the hot air is 0.25MPa, a hot lead plating layer is formed on the surface of the foamy copper, and the thickness of the hot lead plating layer is 50 mu m, so as to prepare the foamy lead;
3) pre-forming a film: taking foamed lead as an anode and stainless steel as a cathode, electrolyzing in a sulfuric acid medium without chloride ions and with the concentration of 5 percent for 4 hours at the current density of 0.5A/square decimeter, and forming a lead dioxide layer on the surface of the foamed lead to prepare a foamed lead substrate;
4) and then preheating: preheating a foamed lead matrix to 130 ℃;
5) and hot lead injection: putting the preheated foamed lead substrate into a mould, wherein the lowest layer is the foamed lead substrate with the surface fully covered with a lead dioxide layer, the middle layer is a titanium net, the upper layer is the foamed lead substrate with the surface fully covered with the lead dioxide layer, closing the mould, vacuumizing to minus 0.1 bar, injecting lead or lead alloy liquid at 350 ℃, preserving the temperature for 1min, enabling the lead or lead alloy liquid to flow into all gaps, filling the gaps and pores, then quickly cooling, solidifying, and forming a hot-cast lead layer on the surface of the lead dioxide layer to obtain the sandwich structure composite lead electrode;
6) anode life test
In 150 g/l aqueous sulfuric acid at 60 ℃ with 100A/dm2Carrying out an accelerated electrolysis test on the sandwich structure composite lead electrode by using the current density, wherein the accelerated life is listed in Table 1;
7) chlorine ion resistance test
Adding hydrochloric acid with chloride ion of 5 g/L into 150 g/L sulfuric acid water solution, and heating at 60 deg.C with 100A/dm2The current density was used to perform an accelerated electrolysis test on the Sandwich-structured composite lead electrode, and the accelerated life was shown in Table 1.
Use of the sandwich structured composite lead electrode of this example: in the use process of the sandwich structure composite lead electrode, because the lead dioxide layer covers the surface of the foamed lead, the compact lead dioxide layer is arranged in the three-dimensional direction of the lead anode, and a lead dioxide protective layer is easily formed in the use process, so the service life is extremely long. A small amount of the fallen micro powder is deposited at the bottom of the tank and recovered, and a small amount of the fallen micro powder is collected by a filter membrane of a filter and then recovered.
The reuse of lead metal of the sandwich structure composite lead electrode of the embodiment: when the sandwich structure composite lead electrode is used, the lead dioxide is gradually increased along with the consumption of the anode, the lead dioxide is dissolved in acetic acid and electroplated on the surface of polyurethane foam to prepare a metal foam lead base material, and the recycling of lead metal is realized. By the method, lead metal can be recycled, and highly toxic lead metal and compounds thereof cannot be discharged to the environment, so that great economic benefit and environmental benefit are obtained.
Example 2.
The preparation method of the sandwich structure composite lead electrode comprises the following preparation steps:
the foam copper with the thickness of 5mm, the pore diameter of 50PPI and the unit area weight of 50 g/square decimeter is selected.
1) Preheating: adopting hot air to preheat the foam copper to 140 ℃, wherein the air temperature of the hot air is 140 ℃, and the air pressure is 0.12 MPa;
2) and hot dip coating: hot dip plating preheated foamy copper in 355 ℃ lead or lead alloy liquid for 9min, blowing the plated foamy copper by a hot air knife, wherein the temperature of hot air is 155 ℃, the pressure of the hot air is 0.30MPa, forming a hot-dip plated lead layer on the surface of the foamy copper, and the thickness of the hot-dip plated lead layer is 100 mu m to obtain foamy lead;
3) pre-forming a film: taking foamed lead as an anode and stainless steel as a cathode, electrolyzing in a sulfuric acid medium without chloride ions and with the concentration of 5 percent for 8 hours at the current density of 0.5A/square decimeter, and forming a lead dioxide layer on the surface of the foamed lead to prepare a foamed lead substrate;
4) and then preheating: preheating a foamed lead matrix to 140 ℃;
5) and hot lead injection: putting the preheated foamed lead substrate into a mould, wherein the lowest layer is the foamed lead substrate with the surface fully covered with a lead dioxide layer, the middle layer is a titanium net, the upper layer is the foamed lead substrate with the surface fully covered with the lead dioxide layer, closing the mould, vacuumizing to minus 0.1 bar, injecting lead or lead alloy liquid at 355 ℃, preserving the temperature for 1min, enabling the lead or lead alloy liquid to flow into all gaps, filling the gaps and pores, then quickly cooling, solidifying, and forming a hot-cast lead layer on the surface of the lead dioxide layer to obtain the sandwich structure composite lead electrode;
6) anode life test
In 150 g/l aqueous sulfuric acid at 60 ℃ with 100A/dm2Carrying out an accelerated electrolysis test on the sandwich structure composite lead electrode by using the current density, wherein the accelerated life is listed in Table 1;
7) chlorine ion resistance test
Adding hydrochloric acid with chloride ion of 5 g/L into 150 g/L sulfuric acid water solution, and heating at 60 deg.C with 100A/dm2The current density was used to perform an accelerated electrolysis test on the Sandwich-structured composite lead electrode, and the accelerated life was shown in Table 1.
Use of the sandwich structured composite lead electrode of this example: in the use process of the sandwich structure composite lead electrode, because the lead dioxide layer covers the surface of the foamed lead, the compact lead dioxide layer is arranged in the three-dimensional direction of the lead anode, and a lead dioxide protective layer is easily formed in the use process, so the service life is extremely long. A small amount of the fallen micro powder is deposited at the bottom of the tank and recovered, and a small amount of the fallen micro powder is collected by a filter membrane of a filter and then recovered.
The reuse of lead metal of the sandwich structure composite lead electrode of the embodiment: when the sandwich structure composite lead electrode is used, the lead dioxide is gradually increased along with the consumption of the anode, the lead dioxide is dissolved in acetic acid and electroplated on the surface of polyurethane foam to prepare a metal foam lead base material, and the recycling of lead metal is realized. By the method, lead metal can be recycled, and highly toxic lead metal and compounds thereof cannot be discharged to the environment, so that great economic benefit and environmental benefit are obtained.
Example 3.
The preparation method of the sandwich structure composite lead electrode comprises the following preparation steps:
the foam copper with the thickness of 5mm, the pore diameter of 50PPI and the unit area weight of 50 g/square decimeter is selected.
1) Preheating: adopting hot air to preheat the foam copper to 130-180 ℃, wherein the air temperature of the hot air is 150 ℃, and the air pressure is 0.13 MPa;
2) and hot dip coating: hot dip plating the preheated foamy copper in lead or lead alloy liquid at 360 ℃ for 8min, blowing the plated foamy copper by a hot air knife, wherein the temperature of hot air is 160 ℃, the pressure of the hot air is 0.35MPa, and forming a hot-dip plated lead layer on the surface of the foamy copper, and the thickness of the hot-dip plated lead layer is 150 mu m to obtain the foamy lead;
3) pre-forming a film: taking foamed lead as an anode and stainless steel as a cathode, electrolyzing in a sulfuric acid medium without chloride ions and with the concentration of 5 percent for 12 hours at the current density of 0.5A/square decimeter, and forming a lead dioxide layer on the surface of the foamed lead to prepare a foamed lead substrate;
4) and then preheating: preheating a foamed lead matrix to 150 ℃;
5) and hot lead injection: putting the preheated foamed lead substrate into a mould, wherein the lowest layer is the foamed lead substrate with the surface fully covered with a lead dioxide layer, the middle layer is a titanium net, the upper layer is the foamed lead substrate with the surface fully covered with the lead dioxide layer, closing the mould, vacuumizing to minus 0.1 bar, injecting lead or lead alloy liquid at 360 ℃, preserving the temperature for 1min, enabling the lead or lead alloy liquid to flow into all gaps, filling the gaps and pores, then quickly cooling, solidifying, and forming a hot-cast lead layer on the surface of the lead dioxide layer to obtain the sandwich structure composite lead electrode;
6) anode life test
In 150 g/l aqueous sulfuric acid at 60 ℃ with 100A/dm2Carrying out an accelerated electrolysis test on the sandwich structure composite lead electrode by using the current density, wherein the accelerated life is listed in Table 1;
7) chlorine ion resistance test
Adding hydrochloric acid with chloride ion of 5 g/L into 150 g/L sulfuric acid water solution, and heating at 60 deg.C with 100A/dm2The current density was used to perform an accelerated electrolysis test on the Sandwich-structured composite lead electrode, and the accelerated life was shown in Table 1.
Use of the sandwich structured composite lead electrode of this example: in the use process of the sandwich structure composite lead electrode, because the lead dioxide layer covers the surface of the foamed lead, the compact lead dioxide layer is arranged in the three-dimensional direction of the lead anode, and a lead dioxide protective layer is easily formed in the use process, so the service life is extremely long. A small amount of the fallen micro powder is deposited at the bottom of the tank and recovered, and a small amount of the fallen micro powder is collected by a filter membrane of a filter and then recovered.
The reuse of lead metal of the sandwich structure composite lead electrode of the embodiment: when the sandwich structure composite lead electrode is used, the lead dioxide is gradually increased along with the consumption of the anode, the lead dioxide is dissolved in acetic acid and electroplated on the surface of polyurethane foam to prepare a metal foam lead base material, and the recycling of lead metal is realized. By the method, lead metal can be recycled, and highly toxic lead metal and compounds thereof cannot be discharged to the environment, so that great economic benefit and environmental benefit are obtained.
Example 4.
The preparation method of the sandwich structure composite lead electrode comprises the following preparation steps:
the foam copper with the thickness of 5mm, the pore diameter of 50PPI and the unit area weight of 50 g/square decimeter is selected.
1) Preheating: adopting hot air to preheat the foam copper to 155 ℃, wherein the air temperature of the hot air is 155 ℃, and the air pressure is 0.14 MPa;
2) and hot dip coating: hot dip plating preheated foamy copper in lead or lead alloy liquid at 365 ℃ for 7min, blowing the plated foamy copper by a hot air knife, wherein the temperature of hot air is 165 ℃, the pressure of the hot air is 0.40MPa, and a hot-dip lead plating layer is formed on the surface of the foamy copper, and the thickness of the hot-dip lead plating layer is 200 mu m to prepare foamy lead;
3) pre-forming a film: taking foamed lead as an anode and stainless steel as a cathode, electrolyzing in a sulfuric acid medium without chloride ions and with the concentration of 5 percent for 16 hours at the current density of 0.5A/square decimeter, and forming a lead dioxide layer on the surface of the foamed lead to prepare a foamed lead substrate;
4) and then preheating: preheating a foamed lead matrix to 155 ℃;
5) and hot lead injection: putting the preheated foamed lead substrate into a mould, wherein the lowest layer is the foamed lead substrate with the surface fully covered with a lead dioxide layer, the middle layer is a titanium net, the upper layer is the foamed lead substrate with the surface fully covered with the lead dioxide layer, closing the mould, vacuumizing to minus 0.1 bar, injecting lead or lead alloy liquid at 365 ℃, preserving the temperature for 1min, enabling the lead or lead alloy liquid to flow into all gaps, filling the gaps and pores, then quickly cooling, solidifying, and forming a hot-cast lead layer on the surface of the lead dioxide layer to obtain the sandwich structure composite lead electrode;
6) anode life test
In 150 g/l aqueous sulfuric acid at 60 ℃ with 100A/dm2Carrying out an accelerated electrolysis test on the sandwich structure composite lead electrode by using the current density, wherein the accelerated life is listed in Table 1;
7) chlorine ion resistance test
Adding hydrochloric acid with chloride ion of 5 g/L into 150 g/L sulfuric acid water solution, and heating at 60 deg.C with 100A/dm2The current density was used to perform an accelerated electrolysis test on the Sandwich-structured composite lead electrode, and the accelerated life was shown in Table 1.
Use of the sandwich structured composite lead electrode of this example: in the use process of the sandwich structure composite lead electrode, because the lead dioxide layer covers the surface of the foamed lead, the compact lead dioxide layer is arranged in the three-dimensional direction of the lead anode, and a lead dioxide protective layer is easily formed in the use process, so the service life is extremely long. A small amount of the fallen micro powder is deposited at the bottom of the tank and recovered, and a small amount of the fallen micro powder is collected by a filter membrane of a filter and then recovered.
The reuse of lead metal of the sandwich structure composite lead electrode of the embodiment: when the sandwich structure composite lead electrode is used, the lead dioxide is gradually increased along with the consumption of the anode, the lead dioxide is dissolved in acetic acid and electroplated on the surface of polyurethane foam to prepare a metal foam lead base material, and the recycling of lead metal is realized. By the method, lead metal can be recycled, and highly toxic lead metal and compounds thereof cannot be discharged to the environment, so that great economic benefit and environmental benefit are obtained.
Example 5.
The preparation method of the sandwich structure composite lead electrode comprises the following preparation steps:
the foam copper with the thickness of 5mm, the pore diameter of 100PPI and the unit area weight of 50 g/square decimeter is selected.
1) Preheating: adopting hot air to preheat the foam copper to 160 ℃, wherein the air temperature of the hot air is 160 ℃, and the air pressure is 0.15 MPa;
2) and hot dip coating: hot dip plating the preheated foamy copper in lead or lead alloy liquid at 370 ℃ for 6min, blowing the plated foamy copper by a hot air knife, wherein the temperature of hot air is 170 ℃, the pressure of the hot air is 0.45MPa, and forming a hot-dip lead plating layer on the surface of the foamy copper, and the thickness of the hot-dip lead plating layer is 50 mu m to obtain the foamy lead;
3) pre-forming a film: taking foamed lead as an anode and stainless steel as a cathode, electrolyzing in a sulfuric acid medium without chloride ions and with the concentration of 5 percent for 4 hours at the current density of 0.5A/square decimeter, and forming a lead dioxide layer on the surface of the foamed lead to prepare a foamed lead substrate;
4) and then preheating: preheating a foamed lead matrix to 160 ℃;
5) and hot lead injection: putting the preheated foamed lead substrate into a mould, wherein the lowest layer is the foamed lead substrate with the surface fully covered with a lead dioxide layer, the middle layer is a titanium net, the upper layer is the foamed lead substrate with the surface fully covered with the lead dioxide layer, closing the mould, vacuumizing to minus 0.1 bar, injecting lead or lead alloy liquid at 370 ℃, preserving the temperature for 1min, enabling the lead or lead alloy liquid to flow into all gaps, filling the gaps and pores, then quickly cooling, solidifying, and forming a hot-cast lead layer on the surface of the lead dioxide layer to obtain the sandwich structure composite lead electrode;
6) anode life test
In 150 g/l aqueous sulfuric acid at 60 ℃ with 100A/dm2Carrying out an accelerated electrolysis test on the sandwich structure composite lead electrode by using the current density, wherein the accelerated life is listed in Table 1;
7) chlorine ion resistance test
Adding hydrochloric acid with chloride ion of 5 g/L into 150 g/L sulfuric acid water solution, and heating at 60 deg.C with 100A/dm2The current density was used to perform an accelerated electrolysis test on the Sandwich-structured composite lead electrode, and the accelerated life was shown in Table 1.
Use of the sandwich structured composite lead electrode of this example: in the use process of the sandwich structure composite lead electrode, because the lead dioxide layer covers the surface of the foamed lead, the compact lead dioxide layer is arranged in the three-dimensional direction of the lead anode, and a lead dioxide protective layer is easily formed in the use process, so the service life is extremely long. A small amount of the fallen micro powder is deposited at the bottom of the tank and recovered, and a small amount of the fallen micro powder is collected by a filter membrane of a filter and then recovered.
The reuse of lead metal of the sandwich structure composite lead electrode of the embodiment: when the sandwich structure composite lead electrode is used, the lead dioxide is gradually increased along with the consumption of the anode, the lead dioxide is dissolved in acetic acid and electroplated on the surface of polyurethane foam to prepare a metal foam lead base material, and the recycling of lead metal is realized. By the method, lead metal can be recycled, and highly toxic lead metal and compounds thereof cannot be discharged to the environment, so that great economic benefit and environmental benefit are obtained.
Example 6.
The preparation method of the sandwich structure composite lead electrode comprises the following preparation steps:
the foam copper with the thickness of 5mm, the pore diameter of 100PPI and the unit area weight of 50 g/square decimeter is selected.
1) Preheating: adopting hot air to preheat the foam copper to 165 ℃, wherein the air temperature of the hot air is 165 ℃, and the air pressure is 0.12 MPa;
2) and hot dip coating: hot dip plating preheated foamy copper in 375 ℃ lead or lead alloy liquid for 6min, blowing the plated foamy copper by a hot air knife, forming a hot-dip plated lead layer on the surface of the foamy copper with the thickness of the hot-dip plated lead layer being 100 mu m at the hot air temperature of 175 ℃ and the hot air pressure of 0.50MPa, and preparing foamy lead;
3) pre-forming a film: taking foamed lead as an anode and stainless steel as a cathode, electrolyzing in a sulfuric acid medium without chloride ions and with the concentration of 5 percent for 8 hours at the current density of 0.5A/square decimeter, and forming a lead dioxide layer on the surface of the foamed lead to prepare a foamed lead substrate;
4) and then preheating: preheating a foamed lead matrix to 165 ℃;
5) and hot lead injection: putting the preheated foamed lead substrate into a mould, wherein the lowest layer is the foamed lead substrate with the surface fully covered with a lead dioxide layer, the middle layer is a titanium net, the upper layer is the foamed lead substrate with the surface fully covered with the lead dioxide layer, closing the mould, vacuumizing to minus 0.1 bar, injecting lead or lead alloy liquid at 375 ℃, preserving the temperature for 1min, enabling the lead or lead alloy liquid to flow into all gaps, filling the gaps and pores, then quickly cooling, solidifying, and forming a hot-cast lead layer on the surface of the lead dioxide layer to obtain the sandwich structure composite lead electrode;
6) anode life test
In 150 g/l aqueous sulfuric acid at 60 ℃ with 100A/dm2Carrying out an accelerated electrolysis test on the sandwich structure composite lead electrode by using the current density, wherein the accelerated life is listed in Table 1;
7) chlorine ion resistance test
Adding hydrochloric acid with chloride ion of 5 g/L into 150 g/L sulfuric acid water solution, and heating at 60 deg.C with 100A/dm2The current density was used to perform an accelerated electrolysis test on the Sandwich-structured composite lead electrode, and the accelerated life was shown in Table 1.
Use of the sandwich structured composite lead electrode of this example: in the use process of the sandwich structure composite lead electrode, because the lead dioxide layer covers the surface of the foamed lead, the compact lead dioxide layer is arranged in the three-dimensional direction of the lead anode, and a lead dioxide protective layer is easily formed in the use process, so the service life is extremely long. A small amount of the fallen micro powder is deposited at the bottom of the tank and recovered, and a small amount of the fallen micro powder is collected by a filter membrane of a filter and then recovered.
The reuse of lead metal of the sandwich structure composite lead electrode of the embodiment: when the sandwich structure composite lead electrode is used, the lead dioxide is gradually increased along with the consumption of the anode, the lead dioxide is dissolved in acetic acid and electroplated on the surface of polyurethane foam to prepare a metal foam lead base material, and the recycling of lead metal is realized. By the method, lead metal can be recycled, and highly toxic lead metal and compounds thereof cannot be discharged to the environment, so that great economic benefit and environmental benefit are obtained.
Example 7.
The preparation method of the sandwich structure composite lead electrode comprises the following preparation steps:
the foam copper with the thickness of 5mm, the pore diameter of 100PPI and the unit area weight of 50 g/square decimeter is selected.
1) Preheating: adopting hot air to preheat the foam copper to 170 ℃, wherein the air temperature of the hot air is 170 ℃, and the air pressure is 0.11 MPa;
2) and hot dip coating: hot dip plating the preheated foamy copper in lead or lead alloy liquid at 380 ℃ for 5min, blowing the plated foamy copper by a hot air knife, wherein the temperature of hot air is 180 ℃, the pressure of the hot air is 0.25MPa, and a hot-dip lead layer with the thickness of 150 mu m is formed on the surface of the foamy copper to prepare the foamy lead;
3) pre-forming a film: taking foamed lead as an anode and stainless steel as a cathode, electrolyzing in a sulfuric acid medium without chloride ions and with the concentration of 5 percent for 12 hours at the current density of 0.5A/square decimeter, and forming a lead dioxide layer on the surface of the foamed lead to prepare a foamed lead substrate;
4) and then preheating: preheating a foamed lead matrix to 170 ℃;
5) and hot lead injection: putting the preheated foamed lead substrate into a mould, wherein the lowest layer is the foamed lead substrate with the surface fully covered with a lead dioxide layer, the middle layer is a titanium net, the upper layer is the foamed lead substrate with the surface fully covered with the lead dioxide layer, closing the mould, vacuumizing to minus 0.1 bar, injecting lead or lead alloy liquid at 380 ℃, preserving the temperature for 1min, enabling the lead or lead alloy liquid to flow into all gaps, filling the gaps and pores, then quickly cooling, solidifying, and forming a hot-cast lead layer on the surface of the lead dioxide layer to obtain the sandwich structure composite lead electrode;
6) anode life test
In 150 g/l aqueous sulfuric acid at 60 ℃ with 100A/dm2Carrying out an accelerated electrolysis test on the sandwich structure composite lead electrode by using the current density, wherein the accelerated life is listed in Table 1;
7) chlorine ion resistance test
Adding chloride ions into 150 g/L sulfuric acid water solution5 g/l hydrochloric acid, at 60 ℃ with 100A/dm2The current density was used to perform an accelerated electrolysis test on the Sandwich-structured composite lead electrode, and the accelerated life was shown in Table 1.
Use of the sandwich structured composite lead electrode of this example: in the use process of the sandwich structure composite lead electrode, because the lead dioxide layer covers the surface of the foamed lead, the compact lead dioxide layer is arranged in the three-dimensional direction of the lead anode, and a lead dioxide protective layer is easily formed in the use process, so the service life is extremely long. A small amount of the fallen micro powder is deposited at the bottom of the tank and recovered, and a small amount of the fallen micro powder is collected by a filter membrane of a filter and then recovered.
The reuse of lead metal of the sandwich structure composite lead electrode of the embodiment: when the sandwich structure composite lead electrode is used, the lead dioxide is gradually increased along with the consumption of the anode, the lead dioxide is dissolved in acetic acid and electroplated on the surface of polyurethane foam to prepare a metal foam lead base material, and the recycling of lead metal is realized. By the method, lead metal can be recycled, and highly toxic lead metal and compounds thereof cannot be discharged to the environment, so that great economic benefit and environmental benefit are obtained.
Example 8.
The preparation method of the sandwich structure composite lead electrode comprises the following preparation steps:
the foam copper with the thickness of 5mm, the pore diameter of 100PPI and the unit area weight of 50 g/square decimeter is selected.
1) Preheating: adopting hot air to preheat the foam copper to 180 ℃, wherein the air temperature of the hot air is 180 ℃, and the air pressure is 0.12 MPa;
2) and hot dip coating: hot dip plating the preheated foamy copper in lead or lead alloy liquid at 370 ℃ for 8min, blowing the plated foamy copper by a hot air knife, wherein the temperature of hot air is 165 ℃, the pressure of the hot air is 0.40MPa, a hot lead plating layer is formed on the surface of the foamy copper, and the thickness of the hot lead plating layer is 200 mu m, thus obtaining the foamy lead;
3) pre-forming a film: taking foamed lead as an anode and stainless steel as a cathode, electrolyzing in a sulfuric acid medium without chloride ions and with the concentration of 5 percent for 16 hours at the current density of 0.5A/square decimeter, and forming a lead dioxide layer on the surface of the foamed lead to prepare a foamed lead substrate;
4) and then preheating: preheating a foamed lead matrix to 180 ℃;
5) and hot lead injection: putting the preheated foamed lead substrate into a mould, wherein the lowest layer is the foamed lead substrate with the surface fully covered with a lead dioxide layer, the middle layer is a titanium net, the upper layer is the foamed lead substrate with the surface fully covered with the lead dioxide layer, closing the mould, vacuumizing to minus 0.1 bar, injecting lead or lead alloy liquid at 370 ℃, preserving the temperature for 1min, enabling the lead or lead alloy liquid to flow into all gaps, filling the gaps and pores, then quickly cooling, solidifying, and forming a hot-cast lead layer on the surface of the lead dioxide layer to obtain the sandwich structure composite lead electrode;
6) anode life test
In 150 g/l aqueous sulfuric acid at 60 ℃ with 100A/dm2Carrying out an accelerated electrolysis test on the sandwich structure composite lead electrode by using the current density, wherein the accelerated life is listed in Table 1;
7) chlorine ion resistance test
Adding hydrochloric acid with chloride ion of 5 g/L into 150 g/L sulfuric acid water solution, and heating at 60 deg.C with 100A/dm2The current density was used to perform an accelerated electrolysis test on the Sandwich-structured composite lead electrode, and the accelerated life was shown in Table 1.
Use of the sandwich structured composite lead electrode of this example: in the use process of the sandwich structure composite lead electrode, because the lead dioxide layer covers the surface of the foamed lead, the compact lead dioxide layer is arranged in the three-dimensional direction of the lead anode, and a lead dioxide protective layer is easily formed in the use process, so the service life is extremely long. A small amount of the fallen micro powder is deposited at the bottom of the tank and recovered, and a small amount of the fallen micro powder is collected by a filter membrane of a filter and then recovered.
The reuse of lead metal of the sandwich structure composite lead electrode of the embodiment: when the sandwich structure composite lead electrode is used, the lead dioxide is gradually increased along with the consumption of the anode, the lead dioxide is dissolved in acetic acid and electroplated on the surface of polyurethane foam to prepare a metal foam lead base material, and the recycling of lead metal is realized. By the method, lead metal can be recycled, and highly toxic lead metal and compounds thereof cannot be discharged to the environment, so that great economic benefit and environmental benefit are obtained.
Comparative example 1
A commercially available lead-silver alloy was used as a comparative anode. The silver content was 1.5%.
Anode life test
These samples were used as anodes in a 150 g/l aqueous sulfuric acid solution at a temperature of 60 ℃ with 100A/dm2The current density was used to perform an accelerated electrolysis test on these samples. Accelerated life is listed in table 1.
Chloride ion resistance test
Using these samples as anodes, 5 g/l hydrochloric acid as chloride ion was added to 150 g/l aqueous sulfuric acid solution and 100A/dm was used at 60 ℃2The current density was used to perform an accelerated electrolysis test on these samples. Accelerated life is listed in table 1.
Comparative example 2
Foamed lead is used as a substrate for fixing lead dioxide powder, the foamed lead is 5mm thick, the pore diameter is 50PPI, the unit area weight is 50 g/square decimeter, and a titanium mesh with the thickness of 1.5 mm and the pore diameter of 5mm multiplied by 5mm is used as a supporting material.
Step one, collecting lead anode slime: collecting the dropped anode mud;
step two, cleaning anode mud: placing anode mud in an inclined drum-type anode bag, inserting an insoluble anode into the inclined drum-type anode bag, electrifying, using 200 g/L sulfuric acid as electrolyte, rotating the drum, enabling the anode mud to rotate in the drum, contacting the anode and conducting electricity, dissolving metal powder such as copper, zinc, cobalt, nickel and the like in the anode mud, separating dissolved metal ions through extraction, electrolyzing the metal ions into pure metal, filtering undissolved lead dioxide powder, and drying the pure metal ions for later use;
thirdly, shaping lead dioxide powder: testing lead dioxide powder particles, determining a ball milling process according to the particle size, ball milling and crushing the lead dioxide powder in a ball mill, drying and sieving to obtain lead dioxide anode powder with the required particle size and sieved by a 50-mesh sieve;
step four, press forming: coating lead dioxide powder on two surfaces of foamed lead, wherein the coating amount of the lead dioxide powder is 50 g/square decimeter, the foamed lead is made of a foamed lead material with the pore size of 50PPI and the thickness of 5mm and the weight of 100 g/square decimeter, and the foamed lead is prepared by adopting a polyurethane foam electrolytic lead plating method; the titanium mesh is used as a middle layer, lead dioxide powder is coated on the foamed lead composite materials on the two surfaces of the foamed lead to be used as the two surfaces to form a sandwich structure, then the assembled lead-lead dioxide composite materials are sent into a die to be heated and pressed for forming, the pressure is 50 kilograms per square centimeter, the pressure is kept for 1 minute, and the temperature is 300 ℃;
fifthly, product shaping: carrying out vacuum hot melting treatment on the preformed lead plate at 320 ℃ for 30 minutes, wherein the vacuum degree is 0.1 bar, the lead powder is slightly melted, the strength is increased, and the lead powder coats the lead dioxide powder to form the sandwich structure composite electrode of metallic lead and lead dioxide/titanium mesh/metallic lead and lead dioxide, so that the product is shaped;
sixthly, testing the service life of the anode
These samples were used as anodes in a 150 g/l aqueous sulfuric acid solution at a temperature of 60 ℃ with 100A/dm2The samples were subjected to accelerated electrolysis tests at current densities, and accelerated lifetimes are listed in table 1;
seventh step, chloride ion resistance test
Using these samples as anodes, 5 g/l hydrochloric acid as chloride ion was added to 150 g/l aqueous sulfuric acid solution and 100A/dm was used at 60 ℃2Current densities accelerated electrolysis tests were performed on these samples and accelerated lifetimes are listed in Table 1.
The test life of the sandwich structure composite lead electrodes prepared in examples 1 to 8 and the test life of the anodes in comparative examples 1 and 2 are shown in table 1.
TABLE 1 Life test acceleration table
Figure BDA0002665434290000191
Figure BDA0002665434290000201
Figure BDA0002665434290000211
Figure BDA0002665434290000221
As can be seen from table 1, comparative example 1 is a common lead-silver alloy anode without lead dioxide, and the life can reach 300 hours without chloride ions; in the solution with chloride ions, the surface of the anode can not form a black film, and the black film is damaged in a short time, and the anode flakes are peeled off from the substrate.
As can be seen from the table 1 and the comparative example 2, the sandwich type titanium mesh/foamed lead/lead dioxide composite electrode anode taking the common foamed lead as the matrix has the service life of 500 hours under the condition of no chloride ions; in the solution with chloride ions, the surface of the anode can form a black film, the service life reaches 450 hours, and the service life is longer.
As can be seen from examples 1 to 8 in table 1, the sandwich type titanium mesh/foamed lead/lead dioxide composite electrode anode with the lead dioxide layer made of the special foamed lead as the substrate and made of the foamed copper as the substrate of the invention can effectively form a film, has a very long accelerated life in a common chloride ion-free sulfuric acid accelerating system, is much longer than that of a lead-silver alloy anode, is similar to that of a foamed lead/lead dioxide composite electrode anode with a titanium substrate, and particularly can form a black film on the surface of the anode in a solution with chloride ions, so that the film can be effectively formed, and has a very long accelerated life, which is much longer than that of a lead alloy anode. Compared with the Sandwich type foamed lead/lead dioxide composite electrode anode with the common foamed lead as the substrate in the comparative example 2, the sandwich type foamed lead/lead dioxide composite electrode has the advantages that the service life is prolonged to a certain extent, the lead dioxide layer on the surface of the foamed lead is ensured to be complete and compact in the lead dioxide film layer on the surface of the foamed lead substrate in the service life testing process, and the manufacturing cost of the preparation method is greatly reduced.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. The utility model provides a sandwich structure composite lead electrode which characterized in that: the composite material comprises two composite layers and a supporting material, wherein the supporting material is a titanium net, and the titanium net is arranged between the two composite layers.
2. The sandwich structured composite lead electrode of claim 1, wherein: the composite layer comprises a substrate, and the surface of the substrate sequentially comprises a hot-dip lead layer, a lead dioxide layer and a hot-melt lead layer from bottom to top.
3. The sandwich structured composite lead electrode of claim 2, wherein: the substrate is a copper foam, the copper foam has a thickness of 5mm, a pore size of 50-100PPI, and a unit area weight of 50 g/m.
4. The sandwich structured composite lead electrode of claim 2, wherein: the thickness of the hot-dip lead coating is 50-200 μm.
5. The method for preparing a sandwich structured composite lead electrode according to any one of claims 1 to 4, wherein: the preparation method comprises the following preparation steps:
1) preheating: preheating the foam copper to 130-180 ℃;
2) and hot dip coating: hot dip plating the preheated foamy copper in lead or lead alloy liquid to form a hot-dip plated lead layer on the surface of the foamy copper so as to prepare foamy lead;
3) pre-forming a film: taking foamed lead as an anode and stainless steel as a cathode, and electrolyzing in a sulfuric acid medium without chloride ions to form a lead dioxide layer on the surface of the foamed lead to prepare a foamed lead substrate;
4) and then preheating: preheating a foamed lead substrate to 130-180 ℃;
5) and hot lead injection: putting the preheated foamed lead substrate into a mould, wherein the lowest layer is the foamed lead substrate with the surface fully covered with a lead dioxide layer, the middle layer is a titanium net, the upper layer is the foamed lead substrate with the surface fully covered with the lead dioxide layer, closing the mould, vacuumizing, injecting lead or lead alloy liquid, preserving heat, enabling the lead or lead alloy liquid to flow into all gaps, filling the gaps and pores, rapidly cooling, solidifying, and forming a hot melt-cast lead layer on the surface of the lead dioxide layer to obtain the sandwich structure composite lead electrode.
6. The method for preparing the sandwich structure composite lead electrode according to claim 5, wherein the method comprises the following steps: the preheating in the step 1) is specifically as follows: the copper foam is preheated to 130-180 ℃ by hot air, the air temperature of the hot air is 130-180 ℃, and the air pressure is 0.10-0.15 MPa.
7. The method for preparing the sandwich structure composite lead electrode according to claim 5, wherein the method comprises the following steps: the step 2) of hot dip coating specifically comprises the following steps: and (3) hot dip plating the preheated foamy copper in lead or lead alloy liquid at 350-380 ℃ for 5-10 min, blowing the plated foamy copper by using a hot air knife, wherein the temperature of the hot air is 150-180 ℃, the pressure of the hot air is 0.25-0.50 MPa, and forming a hot-dip plated lead layer on the surface of the foamy copper to obtain the foamy lead.
8. The method for preparing the sandwich structure composite lead electrode according to claim 5, wherein the method comprises the following steps: the step 3) of pre-filming specifically comprises the following steps: taking foamed lead as an anode and stainless steel as a cathode, electrolyzing in a sulfuric acid medium with the concentration of 5% and without chloride ions, wherein the current density of electrolysis is 0.5A/square decimeter, and the time is 4-16h, and forming a lead dioxide layer on the surface of the foamed lead to prepare the foamed lead substrate.
9. The method for preparing the sandwich structure composite lead electrode according to claim 5, wherein the method comprises the following steps: the step 5) of hot lead injection specifically comprises the following steps: putting the preheated foamed lead substrate into a mould, wherein the lowest layer is the foamed lead substrate with the surface fully covered with a lead dioxide layer, the middle layer is a titanium net, the upper layer is the foamed lead substrate with the surface fully covered with the lead dioxide layer, closing the mould, vacuumizing to minus 0.1 bar, injecting lead or lead alloy liquid at 350-380 ℃, preserving the temperature for 1min, enabling the lead or lead alloy liquid to flow into all gaps, filling the gaps and the pores, then quickly cooling, solidifying, and forming a heat-formed fusion-cast lead layer on the surface of the lead dioxide layer to obtain the sandwich-structured composite lead electrode.
10. The method for preparing the sandwich structure composite lead electrode according to claim 5, wherein the method comprises the following steps: the step 5) is followed by the following steps:
6) anode life test
In 150 g/l aqueous sulfuric acid at 60 ℃ with 100A/dm2Carrying out an accelerated electrolysis test on the sandwich structure composite lead electrode by using the current density;
7) chlorine ion resistance test
Adding hydrochloric acid with chloride ion of 5 g/L into 150 g/L sulfuric acid water solution, and heating at 60 deg.C with 100A/dm2And carrying out an accelerated electrolysis test on the sandwich structure composite lead electrode by using the current density.
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