Plate electrode based on polymer and conductive micro-nano material and preparation method thereof

Abstract

The invention relates to the technical field of plate electrodes, in particular to a plate electrode based on a polymer and a conductive micro-nano material and a preparation method of the plate electrode, the plate electrode comprises the polymer and the conductive micro-nano material, the polymer is one or two of a polymer plate and a polymer emulsion, and the particle size of the conductive micro-nano material is one or more of 40 nm to 10 [mu] m. According to the plate electrode based on the polymer and the conductive micro-nano material and the preparation method of the plate electrode, the plate electrode prepared from the conductive micro-nano materials with different particle sizes has relatively low surface resistivity and relatively high oxygen evolution potential, and can meet application requirements of specific places such as water treatment, electrochemical preparation of graphene and the like.

Description

Technical Field

[0001] The invention relates to the technical field of flat plate electrodes, and in particular to a flat plate electrode based on polymer and conductive micro-nano materials and a preparation method thereof. Background Art

[0002] There is a great demand for electrodes used under harsh conditions, but the actual supply is insufficient. Harsh conditions include use in strong acid, strong alkali, high salt and other environments; oxidation resistance, wide electrochemical window. For example, when electrochemical advanced oxidation is used to treat wastewater, it is hoped that the electrode potential is high and oxygen is not released as much as possible. The electrode must also be resistant to oxidation at high potential. In addition, the electrode also needs to have good conductivity and be moderately priced. Although electrodes made by plating Pt on the surface of some substrates have a certain degree of corrosion resistance, they are expensive and cannot meet the requirements of high oxygen evolution potential. Summary of the invention

[0003] The purpose of the present invention is to provide a flat plate electrode based on polymer and conductive micro-nano materials and a preparation method thereof. The flat plate electrode prepared by conductive micro-nano materials with different particle sizes has a lower surface resistivity and a higher oxygen evolution potential, which can meet the application needs of specific places such as water treatment and electrochemical preparation of graphene.

[0004] To achieve the above objectives, the present invention provides a flat plate electrode based on polymer and conductive micro-nano material, wherein the flat plate electrode comprises a polymer and a conductive micro-nano material, wherein the polymer is one or both of a polymer plate and a polymer emulsion, and the particle size of the conductive micro-nano material is one or more of 40 nm-10 μm.

[0005] Preferably, the polymer includes one or more of PVDF, PTFE and PP, and the polymer emulsion is easy to mix with the conductive micro-nano material.

[0006] The polymer is selected according to the application, such as corrosion resistance, suitable glass transition temperature range, etc. The present invention utilizes the plasticity of the polymer to make the bonding stronger, and at the same time, the required temperature is lower than that of the high temperature sintering process.

[0007] Preferably, the conductive micro-nano material includes boron-doped diamond, titanium carbide, titanium nitride, Ti 4 O 7 , graphene and boron-doped silicon carbide.

[0008] Conductive micro-nano materials meet the requirements of conductivity, corrosion resistance, wide potential window, and moderate price.

[0009] Preferably, the planar electrode further comprises one or more of graphene oxide and carbon nanotubes.

[0010] The size of graphene oxide and carbon nanotubes is micron, submicron or nanometer, or a combination of these sizes, which is convenient for filling pores and maintaining density and conductivity.

[0011] The above-mentioned method for preparing a flat electrode based on polymer and conductive micro-nano materials comprises the following steps: S1. Mix the polymer and the conductive micro-nano material and put them into a ball mill at a ball milling speed of 250-300 rpm for 5-12 h to obtain a slurry; The present invention ball-mills the polymer and the conductive micro-nano material to facilitate uniform mixing of the two.

[0012] S2. Put the slurry obtained in S1 into a mold, and then put them into an oven together, keep them at 100-300°C and 2-10 MPa for 5-10 min, and take out the obtained flat electrode after the mold is cooled.

[0013] Preferably, in S1, the polymer used is a polymer emulsion, and the solid content ratio of the conductive micro-nano material to the polymer in the polymer emulsion is 70:30-85:15.

[0014] The above-mentioned method for preparing a flat electrode based on polymer and conductive micro-nano materials comprises the following steps: S1. Mixing graphene oxide or carbon nanotubes and conductive micro-nano materials to obtain a mixed powder, adding a polymer to the mixed powder and placing the mixed powder in a ball mill at a ball milling speed of 250-300 rpm for 5-12 h to obtain a slurry; S2. Put the slurry obtained in S1 into a mold, and then put them into an oven together, keep them at 100-300°C and 2-10 MPa for 5-10 min, and take out the obtained flat electrode after the mold is cooled.

[0015] Preferably, in S1, the polymer used is a polymer emulsion, and the solid content ratio of graphene oxide or carbon nanotubes and conductive micro-nano materials to the polymer in the polymer emulsion is 70:30-85:15.

[0016] The above-mentioned method for preparing a flat electrode based on polymer and conductive micro-nano materials comprises the following steps: S1. Mixing graphene oxide or carbon nanotubes and conductive micro-nano materials to obtain mixed powders, placing the mixed powders in a ball mill, milling at a speed of 250-300 rpm for 5-12 h to obtain powder; S2, placing the polymer plate into the mold, and then pouring part of the powder obtained in S1 onto the polymer plate to fill the gap between the polymer plate and the mold, and then putting them into an oven together, maintaining them at 100-300°C and 2-10 MPa for 5-10 min, and taking out the semi-finished flat electrode after the mold is cooled; S3. Place the semi-finished flat electrode obtained in S2 into a mold with the uncoated powder side facing upward, pour the remaining powder obtained in S1 onto the polymer plate, maintain at 100-300°C and 2-10 MPa for 5-10 min, and take out the obtained flat electrode after the mold is cooled.

[0017] Preferably, in S1, the solid content ratio of graphene oxide or carbon nanotubes to the conductive micro-nano material is 1.5:98.5.

[0018] Preferably, a skeleton may be added to the flat plate electrode prepared by the present invention, and the skeleton is a titanium mesh.

[0019] Preferably, the flat plate electrode prepared by the present invention is used in water treatment or electrochemical preparation of graphene.

[0020] Therefore, the present invention adopts the above-mentioned flat plate electrode based on polymer and conductive micro-nano material and the preparation method thereof, which has the following beneficial effects: 1. The surface of the flat electrode is a conductive micro-nano material. The small-sized conductive micro-nano material among the conductive micro-nano materials with different particle sizes is filled in the gap of the large-sized conductive micro-nano material. The conductive micro-nano material and the polymer form an interface through bonding; 2. Pressure pressing ensures the close bonding of polymers and conductive micro-nano materials, which is beneficial to electronic conduction. The temperature setting during pressing makes it easier to utilize the plasticity of the polymer to make the bond stronger.

[0021] 3. The flat electrode provided by the present invention has a lower surface resistivity and a higher oxygen evolution potential, which can meet the application needs of specific places such as water treatment and electrochemical preparation of graphene.

[0022] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is the oxygen evolution potential diagram in Example 13 of the present invention. DETAILED DESCRIPTION

[0024] The present invention is further described below in conjunction with the accompanying drawings and embodiments. Unless otherwise defined, the technical terms or scientific terms used in the present invention should be the common meanings understood by people with ordinary skills in the field to which the present invention belongs. The above-mentioned features or features mentioned in the specific examples mentioned in the present invention can be combined arbitrarily, and these specific embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention.

[0025] Example 1 A method for preparing a flat electrode based on polymer and conductive micro-nano materials comprises the following steps: S1, polymer PTFE emulsion and conductive micro-nano material Ti with a particle size of 10 μm 4 O 7 After mixing, the mixture was put into a ball mill at a speed of 250 rpm for 6 h to obtain a slurry; In S1, the polymer used is PTFE emulsion, and the PTFE in the PTFE emulsion is mixed with the conductive micro-nano material Ti 4 O 7 The solid content ratio is 30:70.

[0026] S2. Put the slurry obtained in S1 into a PTFE mold with a length and width of 80 mm and 40 mm respectively, and then put them into an oven together, and keep them at 250°C and 5 MPa for 5 min. After the mold is cooled, take out the obtained flat electrode, which is recorded as TOPF-1.

[0027] Example 2 The difference between this embodiment and embodiment 1 is that the conductive micro-nano material is Ti with a particle size of 10 μm and 1 μm. 4 O 7 The obtained flat plate electrode was obtained by mixing them in a mass ratio of 75:25, and the rest was the same as in Example 1. The obtained flat plate electrode was recorded as TOPF-2.

[0028] Example 3 A method for preparing a flat electrode based on polymer and conductive micro-nano materials comprises the following steps: S1, mixing the polymer PTFE emulsion and the conductive micro-nano material TiC with a particle size of 8 μm, and putting them into a ball mill, with a ball milling speed of 250 rpm and a ball milling time of 6 h to obtain a slurry; In S1, the polymer used is PTFE emulsion, and the solid content ratio of PTFE in the PTFE emulsion to the conductive micro-nano material TiC is 30:70.

[0029] S2. Put the slurry obtained in S1 into a PTFE mold with a length and width of 80 mm and 40 mm respectively, and then put them into an oven together, and keep them at 250°C and 5 MPa for 5 min. After the mold is cooled, take out the obtained flat electrode, which is recorded as TCPF-1.

[0030] Example 4 The difference between this embodiment and embodiment 3 is that the conductive micro-nano material is obtained by mixing TiC with a particle size of 8 μm and 0.8 μm in a mass ratio of 75:25, and the rest is the same as in embodiment 3. The obtained flat electrode is recorded as TCPF-2.

[0031] Example 5 A method for preparing a flat electrode based on polymer and conductive micro-nano materials comprises the following steps: S1, the polymer PTFE emulsion and the conductive micro-nano material TiN with a particle size of 10 μm were mixed and put into a ball mill at a ball milling speed of 250 rpm for 6 h to obtain a slurry; In S1, the polymer used is PTFE emulsion, and the solid content ratio of PTFE in the PTFE emulsion to the conductive micro-nano material TiN is 30:70.

[0032] S2. Put the slurry obtained in S1 into a PTFE mold with a length and width of 80 mm and 40 mm respectively, and then put them into an oven together, and keep them at 250°C and 5 MPa for 5 min. After the mold is cooled, take out the obtained flat electrode, which is recorded as TNPF-1.

[0033] Example 6 The difference between this embodiment and embodiment 5 is that the conductive micro-nano material is obtained by mixing TiN with a particle size of 10 μm and 0.1 μm in a mass ratio of 75:25, and the rest is the same as embodiment 5. The obtained flat electrode is recorded as TNPF-2.

[0034] Example 7 The difference between this embodiment and embodiment 5 is that the conductive micro-nano material is obtained by mixing TiN with particle sizes of 10 μm, 1 μm and 40 nm in a mass ratio of 65:25:10, and the rest is the same as embodiment 5. The obtained flat electrode is recorded as TNPF-3.

[0035] Example 8 A method for preparing a flat electrode based on polymer and conductive micro-nano materials comprises the following steps: S1. Graphene oxide and conductive micro-nano material TiN are mixed to obtain a mixed powder, polymer PTFE emulsion is added to the mixed powder, and the mixed powder is put into a ball mill at a ball milling speed of 250 rpm for 6 h to obtain a slurry; In S1, the conductive micro-nano material is obtained by mixing TiN with particle sizes of 10 μm, 1 μm and 40 nm in a mass ratio of 65:25:10, the solid content of graphene oxide is 3.5%, and the solid content ratio of graphene oxide, conductive micro-nano material and PTFE in the polymer PTFE emulsion is 1:69:30.

[0036] S2. Put the slurry obtained in S1 into a PTFE mold with a length and width of 80 mm and 40 mm respectively, and then put them into an oven together, and keep them at 250°C and 5 MPa for 5 min. After the mold is cooled, take out the obtained flat electrode, which is recorded as TNPF-4.

[0037] Example 9 The difference between this embodiment and embodiment 4 is that the polymer is PVDF emulsion, the temperature of the oven in S2 is 160° C., and the rest is the same as in embodiment 4. The obtained flat electrode is denoted as TCPV-1.

[0038] Example 10 The difference between this embodiment and embodiment 9 is that the polymer is PP emulsion, the temperature of the oven in S2 is 130° C., and the rest is the same as in embodiment 9. The obtained flat electrode is denoted as TCPP-1.

[0039] Embodiment 11 A method for preparing a flat electrode based on polymer and conductive micro-nano materials comprises the following steps: S1, polymer PTFE emulsion, conductive micro-nano material Ti with a particle size of 10 μm 4 O 7 After being mixed with 0.8 μm conductive micro-nano material TiC, it was put into a ball mill with a ball milling speed of 250 rpm and a ball milling time of 6 h to obtain a slurry.

[0040] In S1, the solid content ratio of PTFE to conductive micro-nano material in PTFE emulsion is 30:70, and the conductive micro-nano material Ti with a particle size of 10 μm is 2.5 μm. 4 O 7 The mass ratio of the conductive micro-nano material TiC with a thickness of 0.8 μm is 75:25.

[0041] S2. Put the slurry obtained in S1 into a PTFE mold with a length and width of 80 mm and 40 mm respectively, and then put them into an oven together, and keep them at 250°C and 5 MPa for 5 min. After the mold is cooled, take out the obtained flat electrode, which is recorded as TTPF-1.

[0042] Example 12 The difference between this embodiment and embodiment 8 is that the conductive micro-nano material is a conductive micro-nano material Ti with a particle size of 10 μm.4 O 7 and a conductive micro-nano material TiC with a particle size of 0.8 μm were mixed in a mass ratio of 75:25, and the rest were the same as in Example 8. The obtained flat electrode was recorded as TTPF-2.

[0043] Embodiment 13 A method for preparing a flat electrode based on polymer and conductive micro-nano materials comprises the following steps: S1, graphene oxide, 10 μm conductive micro-nano material Ti 4 O 7 and a conductive micro-nano material TiC with a particle size of 0.8 μm to obtain a mixed powder, the mixed powder was mixed with a polymer PVDF emulsion and then put into a ball mill at a ball milling speed of 250 rpm for 6 h to obtain a slurry; In S1, the solid content ratio of graphene oxide, conductive micro-nano material and PVDF in polymer PVDF emulsion is 1:69:30, and the 10 μm conductive micro-nano material Ti 4 O 7 The mass ratio of the conductive micro-nano material TiC with a thickness of 0.8 μm is 75:25.

[0044] S2, put the polymer PP plate into a PTFE mold with a length and width of 80 mm and 40 mm respectively, and the length, width and thickness of the polymer PP plate are 74 mm, 36 mm and 2 mm respectively. Then pour part of the slurry obtained in S1 on the polymer PP plate and fill the gap between the polymer PP plate and the PTFE mold, and then put them into an oven together, keep them at 130°C and 10 MPa for 10 min, and take out the semi-finished flat electrode after the mold cools down; S3, put the semi-finished flat electrode obtained in S2 into the mold with the side not coated with slurry facing up, and pour the remaining slurry obtained in S1 on the polymer PP plate. Keep it in an oven at 150°C and 10 MPa for 10 min, and take out the obtained flat electrode after the mold cools down. The thickness of the flat electrode is 5.2 mm.

[0045] Embodiment 14 The difference between this embodiment and embodiment 13 is that no polymer PVDF emulsion is added, and the conductive micro-nano material Ti with a particle size of 10 μm is used. 4 O 7 The mass ratio of the conductive micro-nano material TiC with a thickness of 0.8 μm to graphene oxide is 98.5:1.5, and the rest is the same as in Example 13. The thickness of the obtained flat electrode is 5.5 mm.

[0046] Embodiment 15 The difference between this embodiment and embodiment 13 is that in S2, the polymer PP plate is replaced by a titanium mesh with a pore size of 3 mm×6 mm and a length, width and thickness of 314 mm, 174 mm and 1 mm respectively; the length and width of the mold are 320 mm and 180 mm respectively; the temperature in the oven is 140°C; the oven temperature in S3 is 160°C, and the rest is the same as in embodiment 13, and the thickness of the obtained flat electrode is 4.8 mm.

[0047] Test Example 1 a. The surface resistivity of the flat plate electrodes in Examples 1-12 was measured using a four-electrode method. The results are shown in Table 1.

[0048] Table 1. Surface resistivity data of the flat plate electrodes in Examples 1-12

[0049] Referring to the data in Table 1, by comparing Example 1 with Example 2, it can be seen that the two particle sizes of Ti 4 O 7 The surface resistivity of the obtained flat electrode is lower and the conductivity is better. Comparing Example 2 with Example 3, it can be seen that the conductivity of the flat electrode using the conductive micro-nano material of TiC is better than that using the conductive micro-nano material of Ti 4 O 7 A flat plate electrode. Comparing Example 3 with Example 4, it can be seen that the conductivity of the obtained flat plate electrode is better by combining two TiC particle sizes. Comparing Example 5 to Example 7, it can be seen that in Example 7, the conductivity of the obtained flat plate electrode is significantly improved by combining three TiN particle sizes. The graphene oxide introduced in Example 8 can be deoxidized to form graphene at 250°C, so the conductivity of TNPF-4 is significantly improved compared with Example 5 to Example 7.

[0050] It can be seen from Examples 9 and 10 that the use of polymers PVDF and PP can produce flat-plate electrodes at a relatively low temperature, with little effect on the surface conductivity. It can be seen from the comparison between Examples 11 and 12 and Example 1 that the surface conductivity of the flat-plate electrodes obtained in Examples 11 and 12 is better than that of the flat-plate electrodes obtained in Example 1 using only Ti 4 O 7 .

[0051] b. The resistance at each location on the front and back sides of the flat electrode in Examples 13-15 was measured using a multimeter. The resistance at each location in Example 13 was less than 5 Ω, indicating that the conductive powder can form a continuous electron channel on the surface of the polymer PP plate.

[0052] The resistance at each location in Example 14 is less than 5 Ω. Compared with Example 13, it can be seen that the conductive powder is directly hot-pressed onto the surface of the polymer PP without using a polymer emulsion, and a connected electron channel can also be formed.

[0053] The resistance between the front and back surfaces of the flat electrode in Example 15 is less than 5 Ω, indicating that hot pressing the conductive powder on the titanium mesh surface can form a connected electron channel. The flat electrode was placed at an angle of about 80° to the ground for 24 hours, and no obvious deformation was observed, indicating that the flat electrode pressed with the titanium mesh as the skeleton has a certain self-supporting strength and can meet practical applications.

[0054] c. The oxygen evolution curve of the flat electrode in Example 13 was tested in a 60% sulfuric acid solution and compared with that of the Pt electrode. The results are as follows: Figure 1 As shown, it is shown that the flat electrode prepared by this method has a higher oxygen evolution potential, which can meet the application needs of specific places such as water treatment and electrochemical preparation of graphene.

[0055] Therefore, the present invention adopts the above-mentioned flat plate electrode based on polymer and conductive micro-nano materials and its preparation method. The flat plate electrode prepared by mixing conductive micro-nano materials of different particle sizes has a lower surface resistivity and a higher oxygen evolution potential, which can meet the application needs of specific places such as water treatment and electrochemical preparation of graphene.

[0056] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. A flat plate electrode based on polymer and conductive micro-nano materials, characterized in that: The flat plate electrode comprises a polymer and a conductive micro-nano material, the polymer is one or both of a polymer plate and a polymer emulsion, and the particle size of the conductive micro-nano material is one or more of 40 nm-10 μm.

2. A planar electrode based on polymer and conductive micro-nano materials according to claim 1, characterized in that: The polymer includes one or more of PVDF, PTFE and PP.

3. A planar electrode based on polymer and conductive micro-nano materials according to claim 2, characterized in that: The conductive micro-nano material includes one or more of boron-doped diamond, titanium carbide, titanium nitride, Ti4O7, graphene and boron-doped silicon carbide.

4. The planar electrode based on polymer and conductive micro-nano material according to claim 3, characterized in that: The plate electrode further includes one or more of graphene oxide and carbon nanotubes.

5. A method for preparing a planar electrode based on a polymer and a conductive micro-nano material according to any one of claims 1 to 3, characterized in that: The following steps are included: S1. Mix the polymer and the conductive micro-nano material and put them into a ball mill at a ball milling speed of 250-300 rpm for 5-12 h to obtain a slurry; S2. Put the slurry obtained in S1 into a mold, and then put them into an oven together, keep them at 100-300°C and 2-10 MPa for 5-10 min, and take out the obtained flat electrode after the mold is cooled.

6. The method for preparing a planar electrode based on polymer and conductive micro-nano materials according to claim 5, characterized in that: In S1, the polymer used is a polymer emulsion, and the solid content ratio of the conductive micro-nano material to the polymer in the polymer emulsion is 70:30~85:

15.

7. The method for preparing a planar electrode based on polymer and conductive micro-nano materials according to claim 4, characterized in that: The following steps are included: S1. Mixing graphene oxide or carbon nanotubes and conductive micro-nano materials to obtain a mixed powder, adding a polymer to the mixed powder and placing the mixed powder in a ball mill at a ball milling speed of 250-300 rpm for 5-12 h to obtain a slurry; S2. Put the slurry obtained in S1 into a mold, and then put them into an oven together, keep them at 100-300°C and 2-10 MPa for 5-10 min, and take out the obtained flat electrode after the mold is cooled.

8. The method for preparing a planar electrode based on polymer and conductive micro-nano materials according to claim 7, characterized in that: In S1, the polymer used is a polymer emulsion, and the solid content ratio of graphene oxide or carbon nanotubes and conductive micro-nano materials to the polymer in the polymer emulsion is 70:30~85:

15.

9. The method for preparing a planar electrode based on polymer and conductive micro-nano materials according to claim 4, characterized in that: The following steps are included: S1. Mixing graphene oxide or carbon nanotubes and conductive micro-nano materials to obtain mixed powders, placing the mixed powders in a ball mill, milling at a speed of 250-300 rpm for 5-12 h to obtain powder; S2, placing the polymer plate into the mold, and then pouring part of the powder obtained in S1 onto the polymer plate to fill the gap between the polymer plate and the mold, and then putting them into an oven together, maintaining them at 100-300°C and 2-10 MPa for 5-10 min, and taking out the semi-finished flat electrode after the mold is cooled; S3. Place the semi-finished flat electrode obtained in S2 into a mold with the uncoated powder side facing upward, pour the remaining powder obtained in S1 onto the polymer plate, maintain at 100-300°C and 2-10 MPa for 5-10 min, and take out the obtained flat electrode after the mold is cooled.

10. The method for preparing a planar electrode based on polymer and conductive micro-nano materials according to claim 9, characterized in that: In S1, the solid content ratio of graphene oxide or carbon nanotubes and conductive micro-nano materials is 1.5:98.5.

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