Anode material with long service life and preparation method thereof

Abstract

The invention provides a long-service-life anode material and a preparation method thereof, and belongs to the technical field of anode materials.The preparation method comprises the following steps that S1, a copper-aluminum alloy matrix is sequentially subjected to oil removal, galling and erosion treatment, and a pretreated copper-aluminum alloy matrix is obtained; s2, modified Ti4O7, borax and a wetting agent are dispersed in an ethanol solution to obtain a functionalized coating solution, the pretreated copper-aluminum alloy matrix is coated with the functionalized coating solution, the long-life anode material is obtained after calcination, and the modified Ti4O7 is prepared by modifying Ti4O7 through silicon dioxide. According to the method, the copper-aluminum alloy matrix is subjected to chemical erosion, tiny holes are formed in the surface of the copper-aluminum alloy matrix, the adhesion strength of the Ti4O7 material to the matrix is improved, meanwhile, aluminum exposed in the holes is oxidized to form a layer of aluminum oxide film, a Ti4O7 conductive film can be anchored, the integrality and the adhesion capacity of Ti4O7 are improved, the Ti4O7 conductive film is tightly attached to the metal matrix, and the service life of the Ti4O7 conductive film is prolonged. The service life of the electrode material is prolonged.

Description

Technical Field

[0001] The present invention belongs to the technical field of anode materials, and particularly relates to a high-life anode material and a preparation method thereof. Background Art

[0002] As a stable single-phase titanium black, Ti4O7 has high electrical conductivity and chemical stability due to its special crystal structure. Compared with noble metal electrode materials (such as platinum, iridium, etc.), the cost of Ti4O7 is relatively low, and it has high application prospects in electrode materials.

[0003] The copper matrix has good electrical conductivity and is a commonly used electrode matrix. The poor adhesion ability and dispersibility of Ti4O7 result in poor compatibility and bonding ability between the Ti4O7 body and the copper matrix. When the two are used together to prepare an electrode material, it is difficult for Ti4O7 to form a dense conductive layer structure on the surface of the matrix, and the bonding force is poor, which affects its service life during the electrolysis process. Summary of the Invention

[0004] To solve the problems in the background art, the present invention provides a high-life anode material and a preparation method thereof, which can form a uniform and dense Ti4O7 conductive film on the surface of the matrix, effectively improve the adhesion strength of the Ti4O7 material to the matrix, and make the finally prepared electrode material have a high service life.

[0005] To achieve the above object, the present invention provides the following technical solutions: A preparation method of a high-life anode material specifically includes the following steps: S1. First, immerse the copper-aluminum alloy matrix in an alkali solution to remove surface oil stains, rinse it with water, dry it, and then perform a roughening treatment. Then, immerse the copper-aluminum alloy matrix in a chemical etching solution for etching treatment. After the etching is completed, take out the matrix, soak it in a sodium sulfite solution, and dry it to obtain a pretreated copper-aluminum alloy matrix; S2. Disperse the modified Ti4O7, borax, and wetting agent in an ethanol solution to obtain a functionalized coating solution, where the mass ratio of the modified Ti4O7, borax, and wetting agent is 10:0.5 - 1:1 - 2. Coat the functionalized coating solution on the pretreated copper-aluminum alloy matrix, dry it, and calcine it under a protective atmosphere to obtain the high-life anode material. The modified Ti4O7 is prepared by modifying Ti4O7 powder with silica.

[0006] Further, the preparation method of the modified Ti4O7 in step S2 includes the following content: A1. Add tetraethyl orthosilicate to an organic solvent, stir evenly to form a tetraethyl orthosilicate solution, add ammonia water to the organic solvent, and stir evenly to obtain an active solution; A2. Add tetraethyl orthosilicate solution and active solution of the same mass into the Ti4O7 suspension simultaneously, stir and react for 10 - 20 h, wash and dry to obtain modified Ti4O7.

[0007] Further, in step S1, the alkali solution is one or a mixture of two of a sodium phosphate solution and a sodium silicate solution with a temperature of 50 - 60°C and a mass fraction of 3 - 5%.

[0008] Further, in the erosion treatment in step S1, the erosion solution is a mixed solution of chromium trioxide and sulfuric acid with a mass concentration of 20 - 30%. The concentration of chromium trioxide in the mixed solution is 80 - 120 g / L, the temperature of the erosion solution is 55 - 65°C, and the erosion time is 10 - 20 min.

[0009] Further, in step S2, the calcination temperature is 700 - 800°C, the calcination time is 20 - 40 min, and the protective atmosphere is an argon atmosphere.

[0010] Further, in step S2, the wetting agent is one or a mixture of two of carboxymethyl cellulose and sodium alginate.

[0011] Further, in step A1, the mass ratio of tetraethyl orthosilicate to the organic solvent in the tetraethyl orthosilicate solution is 1:3 - 5, and the mass ratio of ammonia water to the organic solvent in the active solution is 1:6 - 10.

[0012] Further, in step A2, the Ti4O7 suspension is a mixed dispersion with a mass ratio of Ti4O7 to the organic solvent of 1:4 - 6.

[0013] Further, in steps A1 and A2, the organic solvent is one or a mixture of two or more of methanol, ethanol, n - propanol, isopropanol, and n - butanol.

[0014] The present invention also provides a high - life anode material prepared by the preparation method in the above technical solution.

[0015] This application has the following beneficial effects: 1. The present invention uses a copper - aluminum alloy as the electrode matrix, and through treatment with a chemical erosion solution, many tiny holes are formed on the surface of the copper - aluminum alloy, improving the adhesion strength of the Ti4O7 material to the copper - aluminum alloy matrix. At the same time, the exposed aluminum in the holes is oxidized to form an alumina film, providing conditions for the close combination of the electrode matrix and the modified Ti4O7.

[0016] 2. By modifying Ti4O7 to make it have high dispersion performance, a uniform and dense conductive film can be formed. At the same time, the introduced silica and alumina in the copper-aluminum alloy matrix have high bonding strength after high-temperature treatment, anchoring the Ti4O7 conductive film, thereby improving the adhesion strength and tight fit of Ti4O7 to the matrix and extending the service life of the electrode material. Detailed implementation manners

[0017] The following further elaborates on this application with reference to the embodiments.

[0018] The raw materials of the embodiments and comparative examples of this application are all ordinary commercially available products unless otherwise specified.

[0019] Embodiment 1 A high-life anode material is prepared by the following steps: S1. First, immerse the copper-aluminum alloy matrix in a sodium phosphate solution with a temperature of 55 °C and a mass fraction of 4% to remove surface oil stains. Rinse it with water, dry it, and then perform a roughening treatment. Immerse the copper-aluminum alloy matrix in a chemical etching solution for etching treatment. The temperature of the etching solution is 60 °C, and the etching time is 15 min. After the etching is completed, take out the matrix and soak it in a sodium sulfite solution with a mass fraction of 2.5% for 10 min, and then dry it to obtain a pretreated copper-aluminum alloy matrix. The etching solution is a mixed solution of chromium trioxide and sulfuric acid with a mass concentration of 25%, and the concentration of chromium trioxide in the mixed solution is 100 g / L; S2. Disperse the modified Ti4O7, borax, and carboxymethyl cellulose in an ethanol solution with a mass concentration of 75% to obtain a functionalized coating solution. The mass ratio of the modified Ti4O7, borax, and carboxymethyl cellulose is 10:0.5:1, and the mass ratio of the modified Ti4O7 to the ethanol solution is 1:0.3. Coat the functionalized coating solution on the pretreated copper-aluminum alloy matrix, dry it, and calcine it in an argon atmosphere. The calcination temperature is 750 °C, and the calcination time is 30 min to obtain the high-life anode material; The preparation method of the modified Ti4O7 in step S2 includes the following: A1. Add tetraethyl orthosilicate to methanol. The mass ratio of tetraethyl orthosilicate to methanol is 1:4, and stir evenly to form a tetraethyl orthosilicate solution. Add ammonia water to methanol. The mass ratio of ammonia water to methanol is 1:8, and stir evenly to obtain an active solution; A2. Drop the same mass of the tetraethyl orthosilicate solution and the active solution into a mixed dispersion liquid with a mass ratio of Ti4O7 to methanol of 1:5 at the same time, stir and react for 15 h, wash, and dry to obtain the modified Ti4O7.

[0020] Embodiment 2 A high-life anode material is prepared by the following steps: S1. First, immerse the copper-aluminum alloy substrate in a sodium silicate solution with a temperature of 50 °C and a mass fraction of 3% to remove the surface oil stains. Rinse it thoroughly with water, dry it, and then perform a roughening treatment. Immerse the copper-aluminum alloy substrate in a chemical etching solution for etching treatment. The temperature of the etching solution is 55 °C, and the etching time is 10 min. After the etching is completed, take out the substrate and soak it in a sodium sulfite solution with a mass fraction of 2% for 5 min, and then dry it to obtain a pretreated copper-aluminum alloy substrate. The etching solution is a mixed solution of chromium trioxide and sulfuric acid with a mass concentration of 20%, and the concentration of chromium trioxide in the mixed solution is 80 g / L; S2. Disperse the modified Ti4O7, borax, and sodium alginate in an ethanol solution with a mass concentration of 75% to obtain a functionalized coating solution. The mass ratio of the modified Ti4O7, borax, and sodium alginate is 10:0.5:1, and the mass ratio of the modified Ti4O7 to the ethanol solution is 1:0.3. Coat the functionalized coating solution onto the pretreated copper-aluminum alloy substrate, dry it, and then calcine it in an argon atmosphere. The calcination temperature is 700 °C, and the calcination time is 20 min to obtain the high-life anode material; The preparation method of the modified Ti4O7 in step S2 includes the following contents: A1. Add tetraethyl orthosilicate to ethanol. The mass ratio of tetraethyl orthosilicate to ethanol is 1:3, and stir evenly to form a tetraethyl orthosilicate solution. Add ammonia water to ethanol. The mass ratio of ammonia water to ethanol is 1:6, and stir evenly to obtain an active solution; A2. Drop the same mass of tetraethyl orthosilicate solution and active solution into a mixed dispersion with a mass ratio of Ti4O7 to ethanol of 1:4 at the same time, stir and react for 10 h, wash, and dry to obtain the modified Ti4O7.

[0021] Example 3 A high-life anode material is prepared by the following steps: S1. First, immerse the copper-aluminum alloy substrate in a sodium phosphate solution with a temperature of 60 °C and a mass fraction of 5% to remove the surface oil stains. Rinse it thoroughly with water, dry it, and then perform a roughening treatment. Immerse the copper-aluminum alloy substrate in a chemical etching solution for etching treatment. The temperature of the etching solution is 65 °C, and the etching time is 20 min. After the etching is completed, take out the substrate and soak it in a sodium sulfite solution with a mass fraction of 3% for 15 min, and then dry it to obtain a pretreated copper-aluminum alloy substrate. The etching solution is a mixed solution of chromium trioxide and sulfuric acid with a mass concentration of 30%, and the concentration of chromium trioxide in the mixed solution is 120 g / L; S2. Disperse the modified Ti4O7, borax, and carboxymethyl cellulose in an ethanol solution with a mass concentration of 75% to obtain a functional coating solution, where the mass ratio of modified Ti4O7, borax, and carboxymethyl cellulose is 10:1:2, and the mass ratio of modified Ti4O7 to the ethanol solution is 1:0.3. Coat the functional coating solution onto the pretreated copper-aluminum alloy substrate, dry it, and calcine it in an argon atmosphere at a calcination temperature of 800 °C for 40 min to obtain the high-life anode material; The preparation method of the modified Ti4O7 in step S2 includes the following: A1. Add tetraethyl orthosilicate to n-propanol, with the mass ratio of tetraethyl orthosilicate to n-propanol being 1:5, stir evenly to form a tetraethyl orthosilicate solution. Add ammonia water to n-propanol, with the mass ratio of ammonia water to n-propanol being 1:10, and stir evenly to obtain an active solution; A2. Drop the same mass of tetraethyl orthosilicate solution and active solution simultaneously into a mixed dispersion with a mass ratio of Ti4O7 to n-propanol of 1:6, stir and react for 20 h, wash, and dry to obtain the modified Ti4O7.

[0022] Example 4 A high-life anode material is prepared by the following steps: S1. First, immerse the copper-aluminum alloy substrate in a sodium silicate solution with a temperature of 50 °C and a mass fraction of 5% to remove surface oil stains, rinse it with water, dry it, and then perform a roughening treatment. Immerse the copper-aluminum alloy substrate in a chemical etching solution for etching treatment. The temperature of the etching solution is 55 °C, and the etching time is 20 min. After the etching is completed, take out the substrate and soak it in a sodium sulfite solution with a mass fraction of 2.5% for 5 min, and then dry it to obtain the pretreated copper-aluminum alloy substrate. The etching solution is a mixed solution of chromium trioxide and sulfuric acid with a mass concentration of 30%, and the concentration of chromium trioxide in the mixed solution is 80 g / L; S2. Disperse the modified Ti4O7, borax, and sodium alginate in an ethanol solution with a mass concentration of 75% to obtain a functional coating solution, where the mass ratio of modified Ti4O7, borax, and sodium alginate is 10:0.5:1.5, and the mass ratio of modified Ti4O7 to the ethanol solution is 1:0.3. Coat the functional coating solution onto the pretreated copper-aluminum alloy substrate, dry it, and calcine it in an argon atmosphere at a calcination temperature of 700 °C for 40 min to obtain the high-life anode material; The preparation method of the modified Ti4O7 in step S2 includes the following: A1. Add tetraethyl orthosilicate to isopropanol, with the mass ratio of tetraethyl orthosilicate to isopropanol being 1:5, stir evenly to form a tetraethyl orthosilicate solution. Add ammonia water to isopropanol, with the mass ratio of ammonia water to isopropanol being 1:10, and stir evenly to obtain an active solution; A2. Add tetraethyl orthosilicate solution and active solution with the same mass dropwise into a mixed dispersion liquid with a mass ratio of Ti4O7 to isopropyl alcohol of 1:5, stir and react for 15 h, wash, and dry to obtain modified Ti4O7.

[0023] Example 5 A high-life anodic material is prepared by the following steps: S1. First, immerse the copper-aluminum alloy matrix in a sodium phosphate solution with a temperature of 60 °C and a mass fraction of 3% to remove surface oil stains, rinse it with water, dry it, and then perform a roughening treatment. Immerse the copper-aluminum alloy matrix in a chemical etching solution for etching treatment. The temperature of the etching solution is 65 °C, and the etching time is 10 min. After the etching is completed, take out the matrix and soak it in a sodium sulfite solution with a mass fraction of 3% for 5 min, and then dry it to obtain a pretreated copper-aluminum alloy matrix. The etching solution is a mixed solution of chromium trioxide and sulfuric acid with a mass concentration of 30%. The concentration of chromium trioxide in the mixed solution is 800 g / L; S2. Disperse modified Ti4O7, borax, and sodium alginate in an ethanol solution with a mass concentration of 75% to obtain a functionalized coating solution. The mass ratio of modified Ti4O7, borax, and sodium alginate is 10:1:2, and the mass ratio of modified Ti4O7 to the ethanol solution is 1:0.3. Coat the functionalized coating solution onto the pretreated copper-aluminum alloy matrix, dry it, and calcine it in an argon atmosphere. The calcination temperature is 750 °C, and the calcination time is 30 min to obtain the high-life anodic material; The preparation method of modified Ti4O7 in step S2 includes the following: A1. Add tetraethyl orthosilicate into n-butanol, and the mass ratio of tetraethyl orthosilicate to n-butanol is 1:3. Stir evenly to form a tetraethyl orthosilicate solution. Add ammonia water into n-butanol, and the mass ratio of ammonia water to n-butanol is 1:6. Stir evenly to obtain an active solution; A2. Add tetraethyl orthosilicate solution and active solution with the same mass dropwise into a mixed dispersion liquid with a mass ratio of Ti4O7 to n-butanol of 1:5, stir and react for 20 h, wash, and dry to obtain modified Ti4O7.

[0024] Comparative Example 1 The difference between this comparative example and Example 1 is only that aluminum is not added to the alloy matrix, that is, the copper-aluminum alloy matrix is replaced with a copper alloy matrix without aluminum.

[0025] Comparative Example 2 The difference between this comparative example and Example 1 is only that Ti4O7 is not subjected to modification treatment, that is, modified Ti4O7 is replaced with ordinary Ti4O7.

[0026] Comparative Example 3 The difference between this comparative example and Example 1 is only that the copper-aluminum alloy matrix is replaced with a copper alloy matrix without aluminum, and at the same time, the modified Ti4O7 is replaced with ordinary Ti4O7.

[0027] Effect verification Using the anode materials prepared in Examples 1-5 and Comparative Examples 1-3 as anodes, a copper plate as the cathode, and an electrode spacing of 10 mm, measure the current density of the electrode in a 1.0 mol / L H2SO4 aqueous solution at 50 °C, starting from zero and increasing by 0.5 A / cm per minute 2 until the current density reaches 4.0 A / cm 2 and maintain a stable current density of 4.0 A / cm 2 for testing. The initial cell voltage is about 4.5 V. When the operating voltage rises to 10 V, it is used as the criterion for evaluating the inactivation of the electrode. The electrolysis time at this time is the life of the electrode.

[0028] Table 1 Result analysis By analyzing Examples 1-5 and Comparative Examples 1-3 and combining the data in Table 1, it can be seen that the anode material prepared by the present invention has a relatively long service life. The specific analysis is as follows: It can be seen from Comparative Example 1 and Example 1 that without the addition of aluminum in the alloy matrix, the service life of the electrode material is significantly reduced, indicating that the addition of aluminum in the alloy matrix forms pores on the matrix surface, making the bonding ability between the Ti4O7 conductive film and the alloy matrix strong, not easily falling off, and capable of extending the service life of the electrode material; It can be seen from Comparative Example 2 and Example 1 that without the modification treatment of Ti4O7, the service life of the electrode material is reduced to a certain extent, indicating that the modification treatment of Ti4O7, by introducing silica, makes it have high dispersion performance, forms a uniform and dense conductive film, improves the integrity of the conductive film, and thus extends the service life of the electrode material; It can be seen from Comprehensive Comparative Examples 1-3 and Example 1 that without the addition of aluminum in the alloy matrix and without the modification treatment of Ti4O7, the service life of the electrode material is significantly reduced, indicating that the modification treatment of Ti4O7 and the addition of aluminum in the matrix can produce a synergistic effect. After introducing silica into Ti4O7, it interacts with the alumina in the matrix, making the Ti4O7 conductive film fit tightly with the matrix, giving it high anti-falling ability, and the combination of the two can significantly extend the service life of the electrode material.

[0029] In addition, it should be noted that among the various specific technical features described in the above specific embodiments, without conflict, they can be combined in any appropriate manner. To avoid unnecessary repetition, the present invention will not separately describe various possible combination methods.

[0030] In addition, any combination can be made among various different embodiments of the present invention, as long as it does not violate the idea of the present invention, and it should equally be regarded as the content disclosed by the present invention.

Claims

1. A method for preparing a long-life anode material, characterized in that: The following steps are involved: S1. The copper-aluminum alloy substrate is immersed in an alkaline solution to remove surface oil stains, rinsed with water, and roughened after drying. The copper-aluminum alloy substrate is then immersed in a chemical etching solution for etching. After the etching is completed, the substrate is taken out and immersed in a sodium sulfite solution, and dried to obtain a pretreated copper-aluminum alloy substrate; S2. The modified Ti4O7, borax and wetting agent are dispersed in an ethanol solution to obtain a functionalized coating solution, wherein the mass ratio of the modified Ti4O7, borax and wetting agent is 10:0.5-1:1-2, and the functionalized coating solution is applied to the pretreated copper-aluminum alloy substrate, dried, and calcined under a protective atmosphere to obtain the long-life anode material; The modified Ti4O7 is prepared by modifying Ti4O7 powder with silicon dioxide.

2. The method for preparing a long-life anode material according to claim 1, characterized in that: The preparation of modified Ti4O7 in step S2 includes the following contents: A1. Add tetraethyl orthosilicate to an organic solvent and stir to form a tetraethyl orthosilicate solution, add aqueous ammonia to the organic solvent and stir to obtain an active solution; A2. Add the same mass of tetraethyl orthosilicate solution and active solution to the Ti4O7 suspension at the same time, stir and react for 10-20 hours, wash and dry to obtain modified Ti4O7.

3. The method for preparing a long-life anode material according to claim 1, characterized in that: The alkaline solution in step S1 is one or a mixture of a sodium phosphate solution and a sodium silicate solution with a temperature of 50-60° C. and a mass fraction of 3-5%.

4. The method for preparing a long-life anode material according to claim 1, characterized in that: In the etching treatment in step S1, the etching solution is a mixture of chromium trioxide and sulfuric acid with a mass concentration of 20-30%, the concentration of chromium trioxide in the mixture is 80-120 g / L, the temperature of the etching solution is 55-65° C., and the etching time is 10-20 min.

5. The method for preparing anode materials with a long service life according to claim 1, characterized in that: In step S2, the calcination temperature is 700-800° C., the calcination time is 20-40 min, and the protective atmosphere is argon atmosphere.

6. The method for preparing anode materials with a long service life according to claim 1, characterized in that: In step S2, the wetting agent is one of carboxymethyl cellulose and sodium alginate or a mixture of the two.

7. The method for preparing anode materials with a long service life according to claim 2, characterized in that: In step A1, the mass ratio of tetraethyl orthosilicate to the organic solvent in the tetraethyl orthosilicate solution is 1:3-5, and the mass ratio of ammonia water to the organic solvent in the active solution is 1:6-10.

8. The method for preparing anode materials with a long service life according to claim 2, characterized in that: The Ti4O7 suspension in step A2 is a mixed dispersion in which the mass ratio of Ti4O7 to organic solvent is 1:4-6.

9. The method for preparing anode materials with a long service life according to claim 2, characterized in that: The organic solvent in steps A1 and A2 is one or a mixture of two or more of methanol, ethanol, n-propanol, isopropanol and n-butanol.

10. A long-life anode material, characterized in that: Prepared by the preparation method described in any one of claims 1 to 9.

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