Preparation method of iron oxide / graphene composite conductive material
By preparing iron oxide/graphene composite materials, the problems of high cost, easy oxidation, and limited conductivity of conductive pigments have been solved, achieving low cost, stable conductivity and color development, which is suitable for industrial applications.
Patent Information
- Application Number
- CN202510966902.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-14
- Publication Date
- 2025-11-07
AI Technical Summary
Existing conductive pigments suffer from high cost, easy oxidation and deterioration, limited conductivity, or scarcity of raw materials. In particular, the combination of traditional metal powders and graphene can easily lead to discontinuities in the conductive network.
An iron oxide/graphene composite conductive material was prepared by using a composite method of iron oxide and graphene oxide. The material was prepared by forming a suspension in deionized water by ultrasound, adding a reducing agent for in-situ reduction, and then annealing at high temperature.
It achieves low cost, stable conductivity and color development, and avoids the problems of easy oxidation of metal powder and discontinuity of conductive network caused by graphene sheet stacking, making it suitable for industrial production.
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Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of composite materials, and particularly relates to a preparation method of an iron oxide / graphene composite conductive material. BACKGROUND
[0002] As a functional filler, conductive pigment has important application value in the fields of antistatic coating, electromagnetic shielding material, electronic component packaging, etc. Traditional conductive pigments mainly rely on metal powder (such as silver powder and copper powder), carbon-based materials (such as carbon black and graphite), or metal oxides (such as tin oxide and indium tin oxide) systems. However, the existing technology has obvious limitations: metal-based materials are high in cost and prone to oxidation and degradation; carbon black has limited conductive performance and requires high addition amount, resulting in a decrease in material mechanical performance; semiconductor materials such as indium tin oxide have transparent conductive properties, but the raw materials are scarce and the preparation process is complex.
[0003] In recent years, iron oxide (Fe2O3) has attracted attention due to its low cost, excellent chemical stability, and moderate conductive properties. Graphene, as a two-dimensional carbon material, has ultra-high theoretical electrical conductivity (about 10 6 S / m) and specific surface area, but when used alone, it is prone to discontinuous conductive network due to stacking of the layers, and the high-purity graphene preparation cost limits its industrial application.
[0004] Therefore, it is a technical problem to be solved in the field to develop a composite conductive material preparation method that is simple in process, controllable in cost, and can realize nanoscale synergistic effect of iron oxide and graphene. SUMMARY
[0005] The technical problem to be solved by the application is to provide a preparation method of an iron oxide / graphene composite conductive material, which is suitable for industrial production due to wide raw material sources, simple preparation method, and low cost.
[0006] To solve the above technical problems, the technical solutions adopted by the application are as follows:
[0007] A preparation method of an iron oxide / graphene composite conductive material, wherein an iron oxide precursor and graphene oxide are dispersed in deionized water for ultrasonic treatment to form a uniform suspension, a reducing agent is then added for in-situ reduction, the obtained product is washed and dried, and then high-temperature annealing is performed to obtain the iron oxide / graphene composite conductive material.
[0008] Further, the mass ratio of the iron oxide precursor to graphene oxide is 3:1.
[0009] Further, the iron oxide precursor is FeCl3 or Fe(NO3)3·9H2O.
[0010] Further, the reducing agent is hydrazine hydrate.
[0011] Further, the mass-volume ratio of the graphene and hydrazine hydrate is 20:1.
[0012] Further, the ultrasonic time is 1h.
[0013] Further, the temperature of the in-situ reduction reaction is 50-90℃, and the time is 6-12h.
[0014] Further, the calcination temperature is 600-700℃, and the annealing time is 0.5-2h.
[0015] Further, the preparation method of the iron oxide / graphene composite conductive material comprises the following steps:
[0016] (1) dispersing iron oxide precursor and graphene oxide with a mass ratio of 2-4:1 in deionized water, ultrasonic for 1-2h to form a uniform suspension, then adding hydrazine hydrate, reducing in-situ at 50-90℃ for 6-12h;
[0017] (2) washing and drying the product obtained in step 1), annealing at 600-700℃ under inert atmosphere for 0.5-2h to obtain the iron oxide / graphene composite conductive material.
[0018] Further, the preparation method of the iron oxide / graphene composite conductive material is prepared to obtain the iron oxide / graphene composite conductive material.
[0019] Compared with the prior art, the present application has the following advantages:
[0020] (1) The present application loads iron oxide on the surface of graphene in the form of chemical bonding by in-situ reduction method, and uses the conductive network of graphene and the red-brown color developing characteristics of iron oxide to break through the problems of single color of traditional conductive pigments and easy oxidation and inactivation of metal powder.
[0021] (2) The graphene of the present application is prepared by ultrasonic method, and the preparation process is simple. High-temperature reduction technology is used to repair graphene lattice defects simultaneously, and the chemical bonding between iron oxide and graphene is enhanced, avoiding the problem of conductive network fracture caused by physical mixing method. DETAILED DESCRIPTION
[0022] The present application will be further illustrated below in combination with specific examples. The examples are implemented on the premise of the technical scheme of the present application, and it should be understood that these examples are only used to illustrate the present application and not used to limit the scope of the present application.
[0023] Example 1
[0024] A preparation method of an iron oxide / graphene composite conductive material comprises the following steps:
[0025] (1) 1.5 g FeCl3 and 0.5 g graphene oxide were dispersed in 200 mL deionized water, ultrasonic for 1 h to form a uniform suspension; then 10 mL hydrazine hydrate was added, and in-situ reduction was carried out at 70℃ for 6 h;
[0026] (2) The product obtained in step (1) was centrifuged, washed with deionized water for three times, and then dried in a 60℃ drying oven for 12 h. Then, the product was annealed at 600℃ for 2 h under the atmosphere of argon to obtain the iron oxide / graphene composite material.
[0027] Example 2
[0028] A preparation method of an iron oxide / graphene composite conductive material, comprising the following steps:
[0029] (1) 1.5 g FeCl3 and 0.5 g graphene oxide were dispersed in 200 mL deionized water, ultrasonic for 1 h to form a uniform suspension; then 10 mL hydrazine hydrate was added, and in-situ reduction was carried out at 50℃ for 12 h;
[0030] (2) The product obtained in step (1) was centrifuged, washed with deionized water for three times, and then dried in a 60℃ drying oven for 12 h. Then, the product was annealed at 600℃ for 2 h under the atmosphere of argon to obtain the iron oxide / graphene composite material.
[0031] Example 3
[0032] A preparation method of an iron oxide / graphene composite conductive material, comprising the following steps:
[0033] (1) 1.5 g FeCl3 and 0.5 g graphene oxide were dispersed in 200 mL deionized water, ultrasonic for 1 h to form a uniform suspension; then 10 mL hydrazine hydrate was added, and in-situ reduction was carried out at 90℃ for 2 h;
[0034] (2) The product obtained in step (1) was centrifuged, washed with deionized water for three times, and then dried in a 60℃ drying oven for 12 h. Then, the product was annealed at 600℃ for 2 h under the atmosphere of argon to obtain the iron oxide / graphene composite material.
[0035] Example 4
[0036] A preparation method of an iron oxide / graphene composite conductive material, comprising the following steps:
[0037] (1) 1.5 g FeCl3 and 0.5 g graphene oxide were dispersed in 200 mL deionized water, ultrasonic for 1 h to form a uniform suspension; then 10 mL hydrazine hydrate was added, and in-situ reduction was carried out at 70℃ for 6 h;
[0038] (2) The product obtained in step (1) is centrifuged, washed with deionized water three times, dried in a 60°C drying oven for 12h, and then annealed at 700°C for 0.5h under an argon atmosphere to obtain the iron oxide / graphene composite material.
[0039] Example 5
[0040] A method for preparing an iron oxide / graphene composite conductive material, comprising the following steps:
[0041] (1) 1.5g Fe(NO3)3·9H2O and 0.5g graphene oxide are dispersed in 200mL deionized water, ultrasonic for 1.5h to form a uniform suspension; then 10mL hydrazine hydrate is added, and in-situ reduction is carried out at 70°C for 6h;
[0042] (2) The product obtained in step (1) is centrifuged, washed with deionized water three times, dried in a 60°C drying oven for 12h, and then annealed at 600°C for 2h under an argon atmosphere to obtain the iron oxide / graphene composite material.
[0043] Comparative Example 1
[0044] A method for preparing an iron oxide / graphene composite conductive material, comprising the following steps:
[0045] (1) 1.5g FeCl3 and 0.5g commercial graphene are dispersed in 200mL deionized water, ultrasonic for 1h to form a uniform suspension; then 10mL hydrazine hydrate is added, and in-situ reduction is carried out at 70°C for 6h;
[0046] (2) The product obtained in step (1) is centrifuged, washed with deionized water three times, dried in a 60°C drying oven for 12h to obtain the iron oxide / graphene composite material.
[0047] The properties of the iron oxide / graphene composite materials prepared in Examples 1-4 and Comparative Example 1 are evaluated. The color value test method: the composite pigment is mixed with transparent resin at a mass ratio of 1:5, coated on a white substrate, and after curing, a uniform film layer is formed for testing, and then an X-Rite Ci64 colorimeter is used to test the color value. The surface resistivity test: the composite pigment is mixed with an insulating substrate at a mass ratio of 1:3, coated on a uniform film layer, and after curing, a 10cm×10cm square is cut and tested using a four-probe tester. Before testing, the surface is cleaned with anhydrous ethanol to eliminate static interference. The results are shown in Table 1.
[0048] Table 1 Properties of the iron oxide / graphene composite materials prepared in Examples 1-4 and Comparative Example 1
[0049]
[0050] From Table 1, it can be seen that the iron oxide / graphene composite prepared in the application has good conductivity, color development and stability.
[0051] From Comparative Example 1 and Examples 2 and 3, it can be seen that when the reduction temperature is lower or the reduction time is shorter, the Fe2O3 loading is insufficient or the graphene defect repair is insufficient, resulting in an increase in resistivity; from Comparative Example 1 and Example 4, it can be seen that when the annealing temperature is too high and the time is shortened, the resistivity is reduced, but the Fe2O3 grains are coarsened, and the color development is reduced; from Comparative Example 1 and Comparative Example 1, it can be seen that the commercial graphene is subjected to annealing technology, resulting in degradation of resistivity, which shows that annealing is necessary for chemical bonding and conductivity improvement.
[0052] The above only describes the preferred embodiments of the present application, and it should be noted that for ordinary skilled persons in the art, several improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.
Claims
1. A method for preparing an iron oxide / graphene composite conductive material, characterized in that: The iron oxide precursor and graphene oxide are dispersed in deionized water to form a uniform suspension by ultrasonic treatment, and then a reducing agent is added to reduce in situ, and the obtained product is washed and dried, and then annealed at high temperature to obtain the iron oxide / graphene composite conductive material.
2. The method of claim 1, wherein the method is characterized by: The mass ratio of the iron oxide precursor to graphene oxide is 3:
1.
3. The method of claim 1, wherein the method further comprises: The iron oxide precursor is FeCl3 or Fe(NO3)3·9H2O. 4. The method of claim 1, wherein the method further comprises: The reducing agent is hydrazine hydrate. 5. The method of claim 1, wherein the method further comprises: The mass / volume ratio of graphene to hydrazine hydrate is 20:
1. 6. The method of claim 1, wherein the method further comprises: The ultrasonic treatment time is 1h. 7.The method of claim 1, wherein the method further comprises: mixing the graphene oxide and the iron oxide to form a mixture; and heating the mixture to form the iron oxide / graphene composite conductive material. The temperature of the in-situ reduction reaction is 50-90℃, and the time is 6-12h. 8.The method of claim 1, wherein the method further comprises: mixing the graphene oxide and the iron oxide to form a mixture; and heating the mixture to form the iron oxide / graphene composite conductive material. The calcination temperature is 600-700℃, and the annealing time is 0.5-2h.
9. The method of claim 1, wherein the iron oxide / graphene composite conductive material is prepared by the steps of: preparing graphene oxide by the Hummers method; preparing an iron oxide / graphene composite conductive material by mixing the graphene oxide with an iron source. The method comprises the following steps: (1) The iron oxide precursor and graphene oxide are dispersed in deionized water at a mass ratio of 2-4:1, ultrasonic treatment is performed for 1-2h to form a uniform suspension, and then hydrazine hydrate is added to reduce in situ at 50-90℃ for 6-12h; (2) The product obtained in step 1) is washed and dried, and then annealed at 600-700℃ in an inert atmosphere for 0.5-2h to obtain the iron oxide / graphene composite conductive material.
10. The method for preparing the iron oxide / graphene composite conductive material according to any one of claims 1-9, wherein the iron oxide / graphene composite conductive material is prepared.