A high-lifetime anode material and its preparation method

Abstract

The present invention provides a high-life anode material and a preparation method thereof, belonging to the technical field of anode materials. The preparation method comprises the following steps: S1. The copper-aluminum alloy matrix is successively subjected to degreasing, burring and etching treatments to obtain a pretreated copper-aluminum alloy matrix; S2. Modified Ti4O7, borax and a wetting agent are dispersed in an ethanol solution to obtain a functional coating solution. The functional coating solution is coated on the pretreated copper-aluminum alloy matrix and calcined to obtain the high-life anode material, wherein the modified Ti4O7 is prepared by modifying Ti4O7 with silicon dioxide. In the present invention, the copper-aluminum alloy matrix is chemically etched to form tiny holes on its surface, so as to improve the adhesion strength of the Ti4O7 material to the matrix. Meanwhile, the exposed aluminum in the holes is oxidized to form an alumina film, which can anchor the Ti4O7 conductive film, improve the integrity and adhesion ability of Ti4O7, make it closely fit with the metal matrix, and extend the service life of the electrode material.

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.), Ti4O7 has a relatively low cost and 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, affecting 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:

[0006] A preparation method of a high-life anode material specifically includes the following steps:

[0007] S1. First, immerse the copper-aluminum alloy matrix in an alkaline solution to remove surface oil stains, rinse it with water until clean, 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;

[0008] 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, and the modified Ti4O7 is prepared by modifying Ti4O7 powder with silicon dioxide.

[0009] Further, the preparation method of the modified Ti4O7 in step S2 includes the following content:

[0010] 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;

[0011] A2. Drop the same mass of tetraethyl orthosilicate solution and active solution into the Ti4O7 suspension simultaneously, stir and react for 10 - 20 h, wash, and dry to obtain modified Ti4O7.

[0012] Further, in step S1, the alkaline 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%.

[0013] Further, in the erosion treatment of 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.

[0014] 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.

[0015] Further, in step S2, the wetting agent is one or a mixture of two of carboxymethyl cellulose and sodium alginate.

[0016] 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.

[0017] 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.

[0018] 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.

[0019] The present invention also provides a high - life anode material prepared by the preparation method in the above - mentioned technical solution.

[0020] This application has the following beneficial effects:

[0021] 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.

[0022] 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 close fit of Ti4O7 to the matrix and extending the service life of the electrode material. Specific embodiments

[0023] The following further describes the present application in detail with reference to embodiments.

[0024] The raw materials of the examples and comparative examples of the present application are all commercially available, except as otherwise specified.

[0025] Example 1

[0026] A high-life anode material is prepared by the following steps:

[0027] 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 minutes. 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 minutes, 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;

[0028] 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 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 minutes to obtain the high-life anode material;

[0029] The preparation method of the modified Ti4O7 in step S2 includes the following:

[0030] A1. Add tetraethyl orthosilicate to methanol, and the mass ratio of tetraethyl orthosilicate to methanol is 1:4. Stir evenly to form a tetraethyl orthosilicate solution. Add ammonia water to methanol, and the mass ratio of ammonia water to methanol is 1:8. Stir evenly to obtain an active solution;

[0031] A2. Drop the same mass of tetraethyl orthosilicate solution and active solution into a mixed dispersion with a mass ratio of Ti4O7 to methanol of 1:5 at the same time, stir and react for 15 hours, wash, and dry to obtain the modified Ti4O7.

[0032] Example 2

[0033] A high - life anode material is prepared by the following steps:

[0034] 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 surface oil stains. Rinse it clean 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%. The concentration of chromium trioxide in the mixed solution is 80 g / L;

[0035] 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 10:0.5:1, 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 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;

[0036] The preparation method of modified Ti4O7 in step S2 includes the following:

[0037] A1. Add tetraethyl orthosilicate to ethanol. The mass ratio of tetraethyl orthosilicate to ethanol is 1:3, 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;

[0038] A2. Drop the same mass of tetraethyl orthosilicate solution and active solution simultaneously into a mixed dispersion with a mass ratio of Ti4O7 to ethanol of 1:4, stir and react for 10 h, wash, and dry to obtain modified Ti4O7.

[0039] Example 3

[0040] A high - life anode material is prepared by the following steps:

[0041] 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. 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;

[0042] 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 10:1:2, 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 under an argon atmosphere. The calcination temperature is 800 °C, and the calcination time is 40 min to obtain the high-life anode material;

[0043] The preparation method of the modified Ti4O7 in step S2 includes the following:

[0044] A1. Add tetraethyl orthosilicate to n-propanol. The mass ratio of tetraethyl orthosilicate to n-propanol is 1:5, stir evenly to form a tetraethyl orthosilicate solution. Add ammonia water to n-propanol. The mass ratio of ammonia water to n-propanol is 1:10, and stir evenly to obtain an active solution;

[0045] A2. Drop the same mass of tetraethyl orthosilicate solution and active solution into a mixed dispersion with a mass ratio of Ti4O7 to n-propanol of 1:6 at the same time, stir and react for 20 h, wash, and dry to obtain the modified Ti4O7.

[0046] Example 4

[0047] A high-life anode material is prepared by the following steps:

[0048] 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 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. 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 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 80 g / L;

[0049] 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, where the mass ratio of the modified Ti4O7, borax and sodium alginate is 10:0.5:1.5, 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 calcine it in an argon atmosphere at a calcination temperature of 700 °C for 40 min to obtain the high-life anode material;

[0050] The preparation method of the modified Ti4O7 in step S2 includes the following:

[0051] A1. Add tetraethyl orthosilicate to isopropanol with a mass ratio of tetraethyl orthosilicate to isopropanol of 1:5, stir evenly to form a tetraethyl orthosilicate solution. Add ammonia water to isopropanol with a mass ratio of ammonia water to isopropanol of 1:10, and stir evenly to obtain an active solution;

[0052] A2. Drop the same mass of tetraethyl orthosilicate solution and active solution simultaneously into a mixed dispersion with a mass ratio of Ti4O7 to isopropanol of 1:5, stir and react for 15 h, wash and dry to obtain the modified Ti4O7.

[0053] Example 5

[0054] A high-life anode material is prepared by the following steps:

[0055] S1. First, immerse the copper-aluminum alloy substrate 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 substrate 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 substrate and soak it in a sodium sulfite solution with a mass fraction of 3% 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 800 g / L;

[0056] 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, where the mass ratio of the modified Ti4O7, borax and sodium alginate is 10:1:2, 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 calcine it in an argon atmosphere at a calcination temperature of 750 °C for 30 min to obtain the high-life anode material;

[0057] The preparation method of the modified Ti4O7 in step S2 includes the following:

[0058] A1. Add tetraethyl orthosilicate to n-butanol. The mass ratio of tetraethyl orthosilicate to n-butanol is 1:3. Stir evenly to form a tetraethyl orthosilicate solution. Add ammonia water to n-butanol. The mass ratio of ammonia water to n-butanol is 1:6. Stir evenly to obtain an active solution;

[0059] 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-butanol of 1:5. Stir and react for 20 h, wash, and dry to obtain modified Ti4O7.

[0060] Comparative Example 1

[0061] The difference between this comparative example and Example 1 is only that no aluminum is added to the alloy matrix, that is, the copper-aluminum alloy matrix is replaced with a copper alloy matrix without aluminum.

[0062] Comparative Example 2

[0063] 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.

[0064] Comparative Example 3

[0065] 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, modified Ti4O7 is replaced with ordinary Ti4O7.

[0066] Effect verification

[0067] Use the anode materials prepared in Examples 1-5 and Comparative Examples 1-3 as the anode, a copper plate as the cathode, and the electrode spacing is 10 mm. Measure the electrode in a 1.0 mol / L H2SO4 aqueous solution at 50 °C. The current density increases from zero 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.

[0068] Table 1

[0069]

[0070] Result analysis

[0071] Analyze Examples 1-5 and Comparative Examples 1-3 and combine the data in Table 1. It can be seen that the anode material prepared by the present invention has a relatively high service life. The specific analysis is as follows:

[0072] 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, enhancing the bonding ability between the Ti4O7 conductive film and the alloy matrix, making it not easy to fall off, and thus capable of extending the service life of the electrode material;

[0073] 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, endows it with high dispersion performance, forms a uniform and dense conductive film, improves the integrity of the conductive film, and thereby extends the service life of the electrode material;

[0074] It can be seen from a comprehensive comparison of 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 greatly 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 a high anti-falling-off ability, and the combination of the two can greatly extend the service life of the electrode material.

[0075] In addition, it should be noted that in the above specific embodiments, the various specific technical features described can be combined in any suitable manner without conflict. To avoid unnecessary repetition, the present invention does not further describe various possible combination methods.

[0076] Furthermore, any combination can be made between various different embodiments of the present invention as long as it does not violate the idea of the present invention, and it should also be regarded as the content disclosed by the present invention.

Claims

1. A preparation method of an anode material with high service life, characterized in that, It includes the following steps: S1. Immerse the copper-aluminum alloy substrate in an alkali solution to remove the surface oil stains, rinse it thoroughly with water, dry it, then perform roughening treatment, and then immerse the copper-aluminum alloy substrate in a chemical etching solution for etching treatment. After the etching is completed, take it out, soak it in a sodium sulfite solution, and dry it to obtain a pretreated copper-aluminum alloy substrate; 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 onto the pretreated copper-aluminum alloy substrate, 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 silicon dioxide.

2. The preparation method of the high-life anode material according to claim 1, characterized in that, The preparation of the modified Ti4O7 in step S2 includes the following: 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. Drop the same mass of the tetraethyl orthosilicate solution and the active solution into the Ti4O7 suspension simultaneously, stir and react for 10 - 20 h, wash, and dry to obtain the modified Ti4O7.

3. The preparation method of the high-life anode material according to claim 1, characterized in that, 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%.

4. The preparation method of the high-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 preparation method of the high-life anode material according to claim 1, wherein, 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.

6. The preparation method of the high-life anode material according to claim 1, characterized in that, In step S2, the wetting agent is one or a mixture of two of carboxymethyl cellulose and sodium alginate.

7. The preparation method of the high-life anode material 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 preparation method of the high-life anode material according to claim 2, characterized in that, In step A2, the Ti4O7 suspension is a mixed dispersion with a mass ratio of Ti4O7 to the organic solvent of 1:4 - 6.

9. The preparation method of the high-life anode material according to claim 2, characterized in that 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.

10. A high-lifetime anode material, characterized in that, Prepared by the preparation method described in any one of claims 1 - 9.

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