Conductive polyaniline composite material and preparation method thereof

Abstract

The present invention relates to the technical field of composite materials, and in particular to a conductive polyaniline composite material and a preparation method thereof. The conductive polyaniline composite material of the present invention comprises: a titanium nitride / titanium dioxide / carbon composite material; and a conductive polyaniline disposed on the surface of the titanium nitride / titanium dioxide / carbon composite material; the titanium nitride / titanium dioxide / carbon composite material comprises: a carbon layer; titanium dioxide fibers disposed on the carbon layer; and a titanium nitride layer disposed on the surface of the titanium dioxide fibers. Compared with the prior art, the conductive polyaniline composite material of the present invention comprises a conductive polyaniline / titanium nitride interface, a titanium nitride / titanium dioxide interface, and a titanium dioxide / carbon interface. The introduction of multiple interface structures breaks the coupling relationship between the Seebeck coefficient and the electrical conductivity of the composite thermoelectric material, thereby significantly improving the thermoelectric performance of the material.

Description

Technical Field

[0001] The present invention relates to the technical field of composite materials, and more particularly to a conductive polyaniline composite material and a preparation method thereof. Background Art

[0002] Thermoelectric materials are functional materials that can convert heat and electricity into each other. Compared to traditional thermal power generation technologies, they have advantages such as no moving parts, no noise, long life, and zero pollutant emissions. Furthermore, thermoelectric materials have a sensitive temperature response, making it possible to utilize low-grade waste heat.

[0003] Currently, inorganic semiconductor materials with narrow band gaps and high Seebeck coefficients are widely studied in the field of thermoelectric materials. Due to their superior thermoelectric properties, thermal conductivity semiconductors are considered ideal thermoelectric materials with practical application potential. However, the high cost, toxicity, and difficulties in synthesis and processing of semiconductor materials have limited their application in many emerging fields. Therefore, the research on low-cost, high-performance flexible thermoelectric materials is of great significance.

[0004] Conductive polymers are a class of polymer materials with conjugated π-bonds that have been chemically or electrochemically "doped" to transform them from insulators into conductors. Due to their low cost, ease of synthesis, ease of processing, and low thermal conductivity, conductive polymers are considered potential thermoelectric materials. Furthermore, compared to inorganic semiconductors, conductive polymers are inherently flexible, significantly broadening the application range of thermoelectric materials. Among them, conductive polyaniline (PAI) has garnered widespread attention due to its ease of preparation, flexible and diverse structure, high environmental stability, and high electrical conductivity, making it one of the most popular organic thermoelectric materials. However, the performance of conductive PAI-based thermoelectric materials remains poor, making practical application difficult.

[0005] The performance of thermoelectric materials is usually expressed by ZT value, ZT = S 2 σT / κ, where S and σ are the Seebeck coefficient and electrical conductivity respectively, κ is the thermal conductivity, T is the absolute temperature, and the power factor is S 2 σ, ZT are dimensionless thermoelectric figures of merit. To further optimize the thermoelectric properties of conductive polyaniline, the introduction of highly conductive fillers with high Seebeck coefficients is often used to enhance the thermoelectric performance. Common fillers include high-conductivity fillers such as carbon nanotubes and metal nanowires, or high-Seebeck coefficient fillers such as BeTe and SnSe. However, due to the classic Wiedemann-Franz law, which states that the Seebeck coefficient and electrical conductivity of a material are coupled, it is difficult to simultaneously increase the Seebeck coefficient and electrical conductivity of polyaniline-based composites, thus limiting further optimization of the thermoelectric properties of polyaniline. Summary of the Invention

[0006] In view of this, the object of the present invention is to provide a conductive polyaniline composite material and a preparation method thereof. The conductive polyaniline composite material of the present invention comprises a conductive polyaniline / titanium nitride interface, a titanium nitride / titanium dioxide interface and a titanium dioxide / carbon interface. The introduction of multiple interface structures breaks the coupling relationship between the Seebeck coefficient and electrical conductivity of the composite thermoelectric material, thereby greatly improving the thermoelectric performance of the material.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] A conductive polyaniline composite material, comprising: a carbon composite material and conductive polyaniline arranged on the surface of the carbon composite material;

[0009] The carbon composite material comprises a carbon material and titanium dioxide fibers arranged on the surface of the carbon material;

[0010] The titanium dioxide fiber comprises a titanium dioxide fiber body and a titanium nitride layer arranged on the titanium dioxide fiber body;

[0011] The mass ratio of the conductive polyaniline to the carbon composite material is 1:(1-8).

[0012] The conductive polyaniline composite material of the present invention is composed of a carbon composite material and conductive polyaniline coated on the surface of the titanium nitride / titanium dioxide / carbon composite material;

[0013] The carbon composite material consists of a carbon layer, a titanium dioxide fiber body distributed on the carbon layer, and a titanium nitride layer coated on the surface of the titanium dioxide fiber body;

[0014] The mass ratio of the conductive polyaniline to the carbon composite material is preferably 1:(2-5), more preferably 1:1:5, 1:3 or 1:2.

[0015] In the present invention, the length direction of the titanium dioxide fibers forms an angle with the surface of the carbon material; and the titanium dioxide fibers are vertically arranged on the surface of the carbon layer.

[0016] In the present invention, the raw material of the carbon layer is selected from one or more of carbon paper, graphene film, carbon nanotube film and porous carbon film, preferably carbon paper;

[0017] The thickness of the carbon layer is 1 to 100 μm;

[0018] The titanium dioxide fiber has a diameter of 50 to 200 nm and a length of 100 to 500 nm;

[0019] The thickness of the titanium nitride layer is 0.2 to 0.4 nm;

[0020] The thickness of the conductive polyaniline is 30-100 nm.

[0021] The present invention also provides a method for preparing the conductive polyaniline composite material, comprising: mixing the conductive polyaniline and the carbon composite material in a solution to obtain the polyaniline composite material.

[0022] In the present invention, the method for preparing the carbon composite material comprises:

[0023] (1) mixing a carbon material and a titanium source, and growing titanium dioxide fibers on the surface of the carbon material using a hydrothermal method to obtain a titanium dioxide / carbon composite material;

[0024] (2) The titanium dioxide / carbon composite material is subjected to nitriding treatment to obtain a carbon composite material.

[0025] In the present invention, the molar ratio of the carbon material to the titanium source is 1:(0.01-0.1), preferably 1:0.05; the step (1) further comprises: washing the carbon material with a solvent, and placing the washed carbon material in a titanium tetrachloride solution for 1-2 hours; the solvent is ethanol; and the concentration of the titanium tetrachloride solution is 0.25M-5M.

[0026] In one embodiment of the present invention, the titanium source is tetrabutyl titanate; the tetrabutyl titanate is mixed with the carbon material in the form of a solution; and the preparation method of the tetrabutyl titanate solution comprises: dissolving 1.5 ml of tetrabutyl titanate in a mixed solution of 40 ml of distilled water and 40 ml of concentrated hydrochloric acid, and stirring for 12 hours.

[0027] In the present invention, the nitriding treatment specifically comprises: heat-treating the titanium dioxide / carbon composite material in an ammonia atmosphere;

[0028] The heat treatment conditions are: starting from room temperature, heating at a rate of 1-5°C·min -1 , after the temperature reaches 1000~1200K, keep it warm for 1~6h.

[0029] In the present invention, the mass ratio of the conductive polyaniline to the carbon composite material is 1:(0.1-15); and the solution is a m-cresol solution, preferably a m-cresol standard solution.

[0030] In the present invention, the preparation method of the conductive polyaniline composite material further includes: mixing the conductive polyaniline and the carbon composite material in a solution, filtering, and vacuum drying; mixing the conductive polyaniline and the carbon composite material in the solution specifically comprises: dissolving the conductive polyaniline in the solution, stirring, and dissolving the carbon composite material in the solution containing the conductive polyaniline, and stirring.

[0031] The present invention has no special requirements for the conductive polyaniline, which can be prepared by conventional methods in the art, or commercially available products can also be used.

[0032] The preparation method of the conductive polyaniline of the present invention preferably comprises: mixing camphorsulfonic acid and emerald polyaniline to obtain conductive polyaniline; the molar ratio of camphorsulfonic acid to emerald polyaniline is (0.5-1):1; the preparation method of the emerald polyaniline comprises: using ammonium persulfate and concentrated hydrochloric acid as an oxidant and a dopant, respectively, to prepare polyaniline by an in-situ aniline polymerization method; mixing aniline with concentrated hydrochloric acid, and then mixing with ammonium persulfate, placing the mixture in a water bath for stirring reaction at a water bath temperature of 0-30°C; after the reaction is completed, standing for 24 hours, filtering to obtain a precipitate, washing the precipitate, and drying to obtain powdered polyaniline; controlling the mass ratio of concentrated hydrochloric acid to aniline to be (10-20):1, preferably 20:1, and the mass ratio of concentrated hydrochloric acid to ammonium persulfate to be (1.5-3):1, preferably 3:1; the concentration of the concentrated hydrochloric acid is 0.8-2 mol·L -1 ; Powdered polyaniline was immersed in an ammonia solution to prepare emerald polyaniline.

[0033] The conductive polyaniline composite material prepared by the present invention comprises: a carbon composite material and conductive polyaniline arranged on the surface of the carbon composite material;

[0034] The carbon composite material comprises a carbon material and titanium dioxide fibers arranged on the surface of the carbon material;

[0035] The titanium dioxide fiber comprises a titanium dioxide fiber body and a titanium nitride layer arranged on the titanium dioxide fiber body;

[0036] The mass ratio of the conductive polyaniline to the carbon composite material is 1:(1-8).

[0037] The conductive polyaniline composite material of the present invention is composed of a carbon composite material and conductive polyaniline coated on the surface of the titanium nitride / titanium dioxide / carbon composite material;

[0038] The carbon composite material consists of a carbon layer, a titanium dioxide fiber body distributed on the carbon layer, and a titanium nitride layer coated on the surface of the titanium dioxide fiber body;

[0039] The mass ratio of the conductive polyaniline to the carbon composite material is preferably 1:(2-5), more preferably 1:1:5, 1:3 or 1:2.

[0040] In the present invention, the length direction of the titanium dioxide fibers forms an angle with the surface of the carbon material; and the titanium dioxide fibers are vertically arranged on the surface of the carbon layer.

[0041] In the present invention, the raw material of the carbon layer is selected from one or more of carbon paper, graphene film, carbon nanotube film and porous carbon film, preferably carbon paper;

[0042] The thickness of the carbon layer is 1 to 100 μm;

[0043] The titanium dioxide fiber has a diameter of 50 to 200 nm and a length of 100 to 500 nm;

[0044] The thickness of the titanium nitride layer is 0.2 to 0.4 nm;

[0045] The thickness of the conductive polyaniline is 30-100 nm.

[0046] The conductive polyaniline composite material of the present invention comprises a conductive polyaniline / titanium nitride interface, a titanium nitride / titanium dioxide interface and a titanium dioxide / carbon interface. The introduction of multiple interface structures breaks the coupling relationship between the Seebeck coefficient and electrical conductivity of the composite thermoelectric material, thereby significantly improving the thermoelectric performance of the material. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 Schematic diagram of the process for preparing a conductive polyaniline composite material according to Example 1 of the present invention;

[0048] Figure 2 is a scanning electron microscope image of the titanium nitride / titanium dioxide / carbon paper prepared in Example 1 of the present invention;

[0049] Figure 3 is a partial magnified scanning electron microscope image of the titanium nitride / titanium dioxide / carbon paper prepared in Example 1 of the present invention;

[0050] Figure 4 is a scanning electron microscope image of the conductive polyaniline composite material prepared in Example 1 of the present invention;

[0051] Figure 5 This is a partial magnified scanning electron microscope image of the conductive polyaniline composite material prepared in Example 1 of the present invention;

[0052] Figure 6 3 is a graph showing the relationship between the conductivity of the conductive polyaniline composite materials prepared in the examples of the present invention and the comparative examples and the duration of the NH3 treatment;

[0053] Figure 7 3 is a graph showing the relationship between the Seebeck coefficient of the conductive polyaniline composite materials prepared in the examples of the present invention and the comparative examples and the duration of the NH3 treatment;

[0054] Figure 8 3 is a graph showing the relationship between the power factor of the conductive polyaniline composite materials prepared in the examples of the present invention and the comparative examples and the duration of the NH3 treatment;

[0055] Figure 9 1 is a graph showing the relationship between the conductivity of the conductive polyaniline composite materials prepared in the examples of the present invention and the comparative examples and the mass fraction of TiO2;

[0056] Figure 102 is a graph showing the relationship between the Seebeck coefficient of the conductive polyaniline composite materials prepared in the examples of the present invention and the comparative examples and the mass fraction of TiO2;

[0057] Figure 11 1 is a graph showing the relationship between the power factor of the conductive polyaniline composite materials prepared in the examples of the present invention and the comparative examples and the mass fraction of TiO2. DETAILED DESCRIPTION

[0058] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0059] In order to further illustrate the present invention, the following examples are provided for detailed description. The raw materials used in the following examples of the present invention are all commercially available commodities.

[0060] The carbon paper in the examples of the present invention was purchased from SGL (Germany).

[0061] The conductivity test in the embodiment of the present invention adopts the four-probe method, and the Seebeck coefficient test adopts the definition method.

[0062] Example 1

[0063] The preparation method of the conductive polyaniline composite material of the present invention is as follows: Figure 1 As shown, the following steps are included:

[0064] (1) Preparation of titanium nitride / titanium dioxide coated carbon paper

[0065] S1: Take 1 g of carbon paper (83 mmol), wash the carbon paper with anhydrous ethanol, and place the washed carbon paper in a titanium tetrachloride solution (the concentration of titanium tetrachloride is 2 M) for 2 h.

[0066] S2: Prepare tetrabutyl titanate as a titanium source and prepare a tetrabutyl titanate solution: Dissolve 3.5 ml of tetrabutyl titanate (10.3 mmol) in a mixture of 20 ml of distilled water and 20 ml of concentrated hydrochloric acid and stir for 12 hours to prepare a tetrabutyl titanate solution (concentration: 0.26 M). Place the carbon paper obtained in step S1 and the prepared tetrabutyl titanate solution in an autoclave and heat to 500 K using a hydrothermal method to grow titanium dioxide nanorods on the carbon paper surface. The reaction time is 5 hours. The resulting composite material is called titanium dioxide / carbon paper. The mass ratio of titanium dioxide to carbon paper in the titanium dioxide / carbon paper is 1:2.

[0067] S3: The titanium dioxide / carbon paper obtained in step S2 is placed in an ammonia atmosphere for heat treatment. The heat treatment conditions are: starting from 300K, the heating rate is 2℃·min -1 The temperature reached 1173K and the heat treatment was carried out for 1 hour to obtain titanium nitride / titanium dioxide / carbon paper. The scanning electron microscope image is shown in FIG. Figure 2 As shown, the enlarged image is Figure 3 shown.

[0068] (2) Preparation of conductive polyaniline

[0069] S1: Ammonium persulfate and concentrated hydrochloric acid were selected as oxidant and dopant, respectively, and polyaniline was prepared by in situ aniline polymerization.

[0070] The steps are as follows: 5g of aniline is added dropwise to 100g of concentrated hydrochloric acid (concentration is 1mol·L -1 ) and stirred evenly to prepare an aniline salt solution, then 33 g of ammonium persulfate was added to the aniline salt solution, and the mixture was placed in a water bath for stirring reaction at a water bath temperature of 20°C. After the reaction was completed, the mixture was allowed to stand for 24 h, filtered, and the precipitate was collected and washed with deionized water and dried for 24 h to obtain powdered polyaniline.

[0071] S2: Immersing the polyaniline prepared in S1 into an ammonia solution to prepare emerald polyaniline.

[0072] S3: Based on the solid-state reaction method, camphorsulfonic acid was selected as the dopant, and 0.5 mol of camphorsulfonic acid and 1 mol of polyaniline were mixed in a mortar by mechanical crushing to dope the emerald polyaniline with proton acid to obtain conductive polyaniline.

[0073] (3) Preparation of conductive polyaniline composites

[0074] S1: Dissolve 1 g of the conductive polyaniline obtained in step (2) in 100 ml of the m-cresol standard solution and stir thoroughly for 12 hours.

[0075] S2: Immerse 5 g of the titanium nitride / titanium dioxide / carbon paper prepared in step (2) into the solution prepared in step S1 and stir thoroughly.

[0076] S3: The solution of S2 was filtered to obtain a conductive polyaniline composite material, and the conductive polyaniline composite material was fully dried under a vacuum environment of 0.001 kPa for 48 hours to obtain a conductive polyaniline composite material.

[0077] The conductive polyaniline composite material prepared by the present invention is composed of a carbon composite material and conductive polyaniline coated on the surface of the carbon composite material; the carbon composite material includes carbon paper and titanium dioxide fibers arranged on the surface of the carbon paper; the titanium dioxide fibers include a titanium dioxide fiber body and a titanium nitride layer coated on the titanium dioxide fiber body. Figure 4 As shown, the enlarged image is Figure 5 As shown, the thickness of the carbon paper is 100 μm; the diameter of the titanium dioxide fiber is 100 nm and the length is 500 nm; the thickness of the titanium nitride layer is 0.4 nm; the thickness of the conductive polyaniline is 50 nm; in the conductive polyaniline composite material, the mass fraction of the conductive polyaniline is 14.9%, the mass fraction of the titanium dioxide fiber is 25.7%, and the mass fraction of the carbon paper is 59.44%. After testing, the parameters of the conductive polyaniline composite material of this embodiment are detailed in Tables 1 and Figure 6-8 , conductivity (σ) is 1825S·cm -1 , Seebeck coefficient (S) is 32μV·K -1 , power factor (S 2 σ) is 185 μW·m -1 ·K -2 .

[0078] Examples 2-6

[0079] In the preparation method of the conductive polyaniline composite material of this embodiment, after the temperature in S3 of step (1) of Example 1 is raised to 1173K, the holding time is set to 2h, 3h, 4h, 5h, and 6h respectively. The other conditions are carried out with reference to those in Example 1. The parameters of the conductive polyaniline composite material obtained are detailed in Tables 1 and Figure 6-8 .

[0080] Table 1

[0081] <![CDATA[Conductivity (S·cm -1 )]]> <![CDATA[Seebeck coefficient (μV·K -1 )]]> Power Factor Example 1 1825 32 185 Example 2 1900 32 195 Example 3 1950 32.5 205 Example 4 1970 33 210 Example 5 1980 34 217 Example 6 1980 34 220

[0082] Example 7

[0083] The preparation method of the conductive polyaniline composite material of this embodiment is as follows: the mass of titanium nitride / titanium dioxide / carbon paper in S2 of step (3) of Example 1 is adjusted to 2 g, and the remaining conditions are carried out with reference to those in Example 1 to prepare a conductive polyaniline composite material, wherein the mass fraction of the conductive polyaniline is 37.2%, the mass fraction of the titanium dioxide fiber is 25.6%, and the mass fraction of the carbon paper is 37.2%. The performance parameters are detailed in Tables 2 and Figure 6-8 .

[0084] Examples 8-12

[0085] In the preparation method of the conductive polyaniline composite material of this embodiment, after the temperature in S3 of step (1) of Example 7 is raised to 1173K, the holding time is set to 2h, 3h, 4h, 5h, and 6h respectively. The other conditions are carried out with reference to those in Example 1. The parameters of the conductive polyaniline composite material obtained are detailed in Tables 2 and Figure 6-8 .

[0086] Table 2

[0087] <![CDATA[Conductivity (S·cm -1 )]]> <![CDATA[Seebeck coefficient (μV·K -1 )]]> Power Factor Example 7 1760 29 150 Example 8 1830 29.5 160 Example 9 1880 30 170 Example 10 1925 30.5 180 Example 11 1950 31 185 Example 12 1950 31 185

[0088] Example 13

[0089] The preparation method of the conductive polyaniline composite material of this embodiment is as follows: the mass of titanium nitride / titanium dioxide / carbon paper in S2 of step (3) of Example 1 is adjusted to 2.5 g, and the remaining conditions are carried out with reference to those in Example 1 to prepare a conductive polyaniline composite material, wherein the mass fraction of the conductive polyaniline is 26%, the mass fraction of the titanium dioxide fiber is 25.7%, and the mass fraction of the carbon paper is 48.3%. The performance parameters are detailed in Tables 3 and Figure 6-8 .

[0090] Examples 14-18

[0091] In the preparation method of the conductive polyaniline composite material of this embodiment, after the temperature in S3 of step (1) of Example 13 is raised to 1173K, the holding time is set to 2h, 3h, 4h, 5h, and 6h respectively. The other conditions are carried out with reference to those in Example 1. The parameters of the conductive polyaniline composite material obtained are detailed in Tables 3 and Figure 6-8 .

[0092] Table 3

[0093]

[0094]

[0095] Comparative Example 1

[0096] The preparation method of the conductive polyaniline composite material of this comparative example is compared with Example 1, except that the heat preservation step of the nitriding treatment in step (1) S3 in Example 1 is omitted, and the composite carbon paper is obtained after the temperature reaches 1173K. The conductive polyaniline composite material is prepared by using the composite carbon paper and the conductive polyaniline. After testing, the parameters of the conductive polyaniline composite material are shown in Table 4 and Figure 6-8 , conductivity (σ) is 1700S·cm -1 , Seebeck coefficient (S) is 31μV·K -1 , power factor (S 2 σ) is 162 μW·m -1 ·K-2 .

[0097] Comparative Example 2

[0098] The preparation method of the conductive polyaniline composite material of this comparative example is compared with Example 1, except that the heat preservation step of the nitriding treatment in step (1) S3 in Example 7 is omitted, and the composite carbon paper is obtained after the temperature reaches 1173K. The conductive polyaniline composite material is prepared by using the composite carbon paper and the conductive polyaniline. After testing, the parameters of the conductive polyaniline composite material are shown in Tables 4 and Figure 6-8 , conductivity (σ) is 1650S·cm -1 , Seebeck coefficient (S) is 28μV·K -1 , power factor (S 2 σ) is 125 μW·m -1 ·K -2 .

[0099] Comparative Example 3

[0100] The preparation method of the conductive polyaniline composite material of this comparative example is compared with Example 1, except that the heat preservation step of the nitriding treatment in step (1) S3 in Example 13 is omitted. After the temperature reaches 1173K, the composite carbon paper is obtained, and the conductive polyaniline composite material is prepared using the composite carbon paper and the conductive polyaniline. After testing, the parameters of the conductive polyaniline composite material are shown in Table 4 and Figure 6-8 , conductivity is 1550S·cm -1 , the Seebeck coefficient (S) is 25.5μV·K -1 , power factor (S 2 σ) is 105 μW·m -1 ·K -2 .

[0101] Table 4

[0102] <![CDATA[Conductivity (S·cm -1 )]]> <![CDATA[Seebeck coefficient (μV·K -1 )]]> Power Factor Comparative Example 1 1700 31 162 Comparative Example 2 1650 28 125 Comparative Example 3 1550 25.5 105

[0103] Comparative Example 4

[0104] The preparation method of the conductive polyaniline composite material of this comparative example is as compared with Example 1, except that step (1) of Example 1 is omitted and the remaining steps are carried out with reference to the steps in Example 1. The conductive polyaniline composite material is directly prepared by directly combining carbon paper and conductive polyaniline. In the conductive polyaniline composite material, the mass fraction of conductive polyaniline is 20% and the mass fraction of carbon paper is 80%. After testing, the parameters of the conductive polyaniline composite material of this comparative example are detailed in Tables 5 and Figure 9-11 , conductivity (σ) is 3000S·cm -1 , Seebeck coefficient (S) is 18μV·K -1 , power factor (S 2σ) is 95 μW·m -1 ·K -2 .

[0105] Comparative Example 5

[0106] The preparation method of the conductive polyaniline composite material of this comparative example is as compared with Example 1, except that S3 of step (1) of Example 1 is omitted, the content of tetrabutyl titanate is adjusted to 1.5 ml, and the remaining processes are carried out with reference to the steps in Example 1. The composite carbon paper and conductive polyaniline are used to prepare a conductive polyaniline composite material. In the conductive polyaniline composite material, the mass fraction of the conductive polyaniline is 20%, the mass fraction of the composite carbon paper is 80%, and the mass fraction of the titanium dioxide fiber in the composite carbon paper is 10%.

[0107] After testing, the performance parameters of the conductive polyaniline composite material of this comparative example are shown in Table 5 and Figure 9-11 , conductivity (σ) is 2500S·cm -1 , Seebeck coefficient (S) is 25μV·K -1 , power factor (S 2 σ) is 155 μW·m -1 ·K -2 .

[0108] Comparative Example 6

[0109] The preparation method of the conductive polyaniline composite material in this comparative example is as compared with Example 1, except that S3 of step (1) of Example 1 is omitted, and the remaining processes are carried out with reference to the steps in Example 1. The composite carbon paper and the conductive polyaniline are used to prepare the conductive polyaniline composite material. In the conductive polyaniline composite material, the mass fraction of the conductive polyaniline is 20%, the mass fraction of the composite carbon paper is 80%, and the mass fraction of the titanium dioxide fiber in the composite carbon paper is 25%.

[0110] After testing, the parameters of the conductive polyaniline composite material of this comparative example are shown in Table 5 and Figure 9-11 , conductivity (σ) is 1700S·cm -1 , Seebeck coefficient (S) is 31μV·K -1 , power factor (S 2 σ) is 165 μW·m -1 ·K -2 .

[0111] Comparative Example 7

[0112] The preparation method of the conductive polyaniline composite material in this comparative example is as compared with Example 1, except that S3 of step (1) of Example 1 is omitted, the content of tetrabutyl titanate is adjusted to 5 ml, and the remaining processes are carried out with reference to the steps in Example 1. The composite carbon paper and the conductive polyaniline are used to prepare the conductive polyaniline composite material. In the conductive polyaniline composite material, the mass fraction of the conductive polyaniline is 20%, the mass fraction of the composite carbon paper is 80%, and the mass fraction of the titanium dioxide fiber in the composite carbon paper is 55%.

[0113] After testing, the parameters of the conductive polyaniline composite material of this comparative example are shown in Table 5 and Figure 9-11 , conductivity (σ) is 1100S·cm -1 , Seebeck coefficient (S) is 36μV·K -1 , power factor (S 2 σ) is 142 μW·m -1 ·K -2 .

[0114] Comparative Example 8

[0115] The preparation method of the conductive polyaniline composite material in this comparative example is as compared with Example 1, except that S3 of step (1) of Example 1 is omitted, the content of tetrabutyl titanate is adjusted to 7 ml, and the remaining processes are carried out with reference to the steps in Example 1. The composite carbon paper and the conductive polyaniline are used to prepare the conductive polyaniline composite material. In the conductive polyaniline composite material, the mass fraction of the conductive polyaniline is 20%, the mass fraction of the composite carbon paper is 80%, and the mass fraction of the titanium dioxide fiber in the composite carbon paper is 72%.

[0116] After testing, the parameters of the conductive polyaniline composite material of this comparative example are shown in Table 5 and Figure 9-11 , conductivity (σ) is 800S·cm -1 , Seebeck coefficient (S) is 40μV·K -1 , power factor (S 2 σ) is 120 μW·m -1 ·K -2 .

[0117] Comparative Example 9

[0118] The preparation method of the conductive polyaniline composite material in this comparative example is as compared with Example 1, except that S3 of step (1) of Example 1 is omitted, the content of tetrabutyl titanate is adjusted to 8 ml, and the remaining processes are carried out with reference to the steps in Example 1. The composite carbon paper and the conductive polyaniline are used to prepare the conductive polyaniline composite material. In the conductive polyaniline composite material, the mass fraction of the conductive polyaniline is 20%, the mass fraction of the composite carbon paper is 80%, and the mass fraction of the titanium dioxide fiber in the composite carbon paper is 86%.

[0119] After testing, the parameters of the conductive polyaniline composite material of this comparative example are shown in Table 5 and Figure 9-11 , conductivity (σ) is 400S·cm -1 , the Seebeck coefficient (S) is 43μV·K -1 , power factor (S 2 σ) is 110 μW·m -1 ·K -2 .

[0120] Table 5

[0121] <![CDATA[Conductivity (S·cm -1 )]]> <![CDATA[Seebeck coefficient (μV·K -1 )]]> Power Factor Comparative Example 4 3000 18 95 Comparative Example 5 2500 25 155 Comparative Example 6 1700 31 165 Comparative Example 7 1100 36 142 Comparative Example 8 800 40 120 Comparative Example 9 400 43 110

[0122] Comparative Example 10

[0123] The preparation method of the conductive polyaniline composite material of this comparative example is as compared with Example 7, except that step (1) of Example 1 is omitted and the remaining steps are carried out with reference to the steps in Example 1. The conductive polyaniline composite material is directly prepared by directly combining carbon paper and conductive polyaniline. In the conductive polyaniline composite material, the mass fraction of conductive polyaniline is 50% and the mass fraction of carbon paper is 50%. After testing, the parameters of the conductive polyaniline composite material of this comparative example are detailed in Tables 6 and Figure 9-11 , conductivity (σ) is 2890S·cm -1 , Seebeck coefficient (S) is 16μV·K -1 , power factor (S 2 σ) is 67 μW·m -1 ·K -2 .

[0124] Comparative Example 11

[0125] The preparation method of the conductive polyaniline composite material of this comparative example is as compared with Example 7, except that S3 of step (1) of Example 1 is omitted, the content of tetrabutyl titanate is adjusted to 1.5 ml, and the remaining processes are carried out with reference to the steps in Example 1. The composite carbon paper and conductive polyaniline are used to prepare a conductive polyaniline composite material. In the conductive polyaniline composite material, the mass fraction of the conductive polyaniline is 50%, the mass fraction of the composite carbon paper is 50%, and the mass fraction of the titanium dioxide fiber in the composite carbon paper is 10%.

[0126] After testing, the parameters of the conductive polyaniline composite material of this comparative example are shown in Table 6 and Figure 9-11 , conductivity (σ) is 2390S·cm -1 , Seebeck coefficient (S) is 20μV·K -1 , power factor (S 2 σ) is 96 μW·m -1 ·K -2 .

[0127] Comparative Example 12

[0128] The preparation method of the conductive polyaniline composite material in this comparative example is compared with Example 7, except that S3 of step (1) of Example 1 is omitted, and the remaining processes are carried out with reference to the steps in Example 1. The composite carbon paper and conductive polyaniline are used to prepare a conductive polyaniline composite material. In the conductive polyaniline composite material, the mass fraction of the conductive polyaniline is 50%, the mass fraction of the composite carbon paper is 50%, and the mass fraction of the titanium dioxide fiber in the composite carbon paper is 25%.

[0129] After testing, the parameters of the conductive polyaniline composite material of this comparative example are shown in Table 6 and Figure 9-11 , conductivity (σ) is 1680S·cm -1 , Seebeck coefficient (S) is 25μV·K -1 , power factor (S 2 σ) is 105 μW·m -1 ·K -2 .

[0130] Comparative Example 13

[0131] The preparation method of the conductive polyaniline composite material in this comparative example is as compared with Example 7, except that S3 of step (1) of Example 1 is omitted, the content of tetrabutyl titanate is adjusted to 5 ml, and the remaining processes are carried out with reference to the steps in Example 1. The composite carbon paper and conductive polyaniline are used to prepare a conductive polyaniline composite material. In the conductive polyaniline composite material, the mass fraction of the conductive polyaniline is 50%, the mass fraction of the composite carbon paper is 50%, and the mass fraction of the titanium dioxide fiber in the composite carbon paper is 55%.

[0132] After testing, the parameters of the conductive polyaniline composite material of this comparative example are shown in Table 6 and Figure 9-11 , conductivity (σ) is 1200S·cm -1 , Seebeck coefficient (S) is 30μV·K -1 , power factor (S 2 σ) is 100 μW·m -1 ·K -2 .

[0133] Comparative Example 14

[0134] The preparation method of the conductive polyaniline composite material in this comparative example is as compared with Example 7, except that S3 of step (1) of Example 1 is omitted, the content of tetrabutyl titanate is adjusted to 7 ml, and the remaining processes are carried out with reference to the steps in Example 1. The composite carbon paper and the conductive polyaniline are used to prepare a conductive polyaniline composite material. In the conductive polyaniline composite material, the mass fraction of the conductive polyaniline is 50%, the mass fraction of the composite carbon paper is 50%, and the mass fraction of the titanium dioxide fiber in the composite carbon paper is 72%.

[0135] After testing, the parameters of the conductive polyaniline composite material of this comparative example are shown in Table 6 and Figure 9-11 , conductivity (σ) is 850S·cm -1 , Seebeck coefficient (S) is 34μV·K -1 , power factor (S 2 σ) is 95 μW·m -1 ·K -2 .

[0136] Comparative Example 15

[0137] The preparation method of the conductive polyaniline composite material in this comparative example is as compared with Example 7, except that S3 of step (1) of Example 1 is omitted, the content of tetrabutyl titanate is adjusted to 8 ml, and the remaining processes are carried out with reference to the steps in Example 1. The composite carbon paper and the conductive polyaniline are used to prepare a conductive polyaniline composite material. In the conductive polyaniline composite material, the mass fraction of the conductive polyaniline is 50%, the mass fraction of the composite carbon paper is 50%, and the mass fraction of the titanium dioxide fiber in the composite carbon paper is 86%.

[0138] After testing, the parameters of the conductive polyaniline composite material of this comparative example are shown in Table 6 and Figure 9-11 , conductivity (σ) is 700S·cm -1 , Seebeck coefficient (S) is 36μV·K -1 , power factor (S 2 σ) is 90 μW·m -1 ·K -2 .

[0139] Table 6

[0140] <![CDATA[Conductivity (S·cm -1 )]]> <![CDATA[Seebeck coefficient (μV·K -1 )]]> Power Factor Comparative Example 10 2890 16 67 Comparative Example 11 2390 20 96 Comparative Example 12 1680 25 105 Comparative Example 13 1200 30 100 Comparative Example 14 850 34 95 Comparative Example 15 700 36 90

[0141] Comparative Example 16

[0142] The preparation method of the conductive polyaniline composite material of this comparative example is as compared with Example 13, except that step (1) of Example 1 is omitted and the remaining steps are carried out with reference to the steps in Example 1. The conductive polyaniline composite material is directly prepared by directly combining carbon paper and conductive polyaniline. In the conductive polyaniline composite material, the mass fraction of conductive polyaniline is 35% and the mass fraction of carbon paper is 65%. After testing, the parameters of the conductive polyaniline composite material of this comparative example are detailed in Tables 7 and Figure 9-11 , conductivity (σ) is 2700S·cm -1 , Seebeck coefficient (S) is 13μV·K -1 , power factor (S 2 σ) is 45 μW·m -1 ·K -2 .

[0143] Comparative Example 17

[0144] The preparation method of the conductive polyaniline composite material of this comparative example is compared with Example 13, except that S3 of step (1) of Example 1 is omitted, the content of tetrabutyl titanate is adjusted to 1.5 ml, and the remaining processes are carried out with reference to the steps in Example 1. The composite carbon paper and conductive polyaniline are used to prepare a conductive polyaniline composite material. In the conductive polyaniline composite material, the mass fraction of the conductive polyaniline is 35%, the mass fraction of the carbon paper is 65%, and the mass fraction of the titanium dioxide fiber in the composite carbon paper is 10%.

[0145] After testing, the parameters of the conductive polyaniline composite material of this comparative example are shown in Table 7 and Figure 9-11 , conductivity (σ) is 2200S·cm -1 , Seebeck coefficient (S) is 18μV·K -1 , power factor (S 2 σ) is 72 μW·m -1 ·K -2 .

[0146] Comparative Example 18

[0147] The preparation method of the conductive polyaniline composite material of this comparative example is as compared with Example 13, except that S3 of step (1) of Example 1 is omitted, and the remaining steps are carried out with reference to the steps in Example 1. The composite carbon paper and the conductive polyaniline are used to prepare the conductive polyaniline composite material. In the conductive polyaniline composite material, the mass fraction of the conductive polyaniline is 35%, the mass fraction of the carbon paper is 65%, and the mass fraction of the titanium dioxide fiber in the composite carbon paper is 25%. After testing, the parameters of the conductive polyaniline composite material of this comparative example are detailed in Tables 7 and Figure 9-11 , conductivity (σ) is 1600S·cm -1 , Seebeck coefficient (S) is 22μV·K -1, power factor (S 2 σ) is 75 μW·m -1 ·K -2 .

[0148] Comparative Example 19

[0149] The preparation method of the conductive polyaniline composite material of this comparative example is as compared with Example 13, except that S3 of step (1) of Example 1 is omitted, the content of tetrabutyl titanate is adjusted to 5 ml, and the remaining processes are carried out with reference to the steps in Example 1. The composite carbon paper and conductive polyaniline are used to prepare a conductive polyaniline composite material. In the conductive polyaniline composite material, the mass fraction of the conductive polyaniline is 35%, the mass fraction of the carbon paper is 65%, and the mass fraction of the titanium dioxide fiber in the composite carbon paper is 55%.

[0150] After testing, the parameters of the conductive polyaniline composite material of this comparative example are shown in Table 7 and Figure 9-11 , conductivity (σ) is 1210S·cm -1 , Seebeck coefficient (S) is 26μV·K -1 , power factor (S 2 σ) is 78 μW·m -1 ·K -2 .

[0151] Comparative Example 20

[0152] The preparation method of the conductive polyaniline composite material of this comparative example is as compared with Example 13, except that S3 of step (1) of Example 1 is omitted, the content of tetrabutyl titanate is adjusted to 7 ml, and the remaining processes are carried out with reference to the steps in Example 1. The composite carbon paper and the conductive polyaniline are used to prepare the conductive polyaniline composite material. In the conductive polyaniline composite material, the mass fraction of the conductive polyaniline is 35%, the mass fraction of the carbon paper is 65%, and the mass fraction of the titanium dioxide fiber in the composite carbon paper is 72%. After testing, the parameters of the conductive polyaniline composite material of this comparative example are detailed in Tables 7 and Figure 9-11 , conductivity (σ) is 890S·cm -1 , Seebeck coefficient (S) is 30μV·K -1 , power factor (S 2 σ) is 85 μW·m -1 ·K -2 .

[0153] Comparative Example 21

[0154] The preparation method of the conductive polyaniline composite material of this comparative example is as compared with Example 13, except that S3 of step (1) of Example 1 is omitted, the content of tetrabutyl titanate is adjusted to 8 ml, and the remaining processes are carried out with reference to the steps in Example 1. The composite carbon paper and the conductive polyaniline are used to prepare the conductive polyaniline composite material. In the conductive polyaniline composite material, the mass fraction of the conductive polyaniline is 35%, the mass fraction of the carbon paper is 65%, and the mass fraction of the titanium dioxide fiber in the composite carbon paper is 86%. After testing, the parameters of the conductive polyaniline composite material of this comparative example are detailed in Tables 7 and Figure 9-11 , conductivity (σ) is 800S·cm -1 , Seebeck coefficient (S) is 32μV·K -1 , power factor (S 2 σ) is 88 μW·m -1 ·K -2 .

[0155] Table 7

[0156] <![CDATA[Conductivity (S·cm -1 )]]> <![CDATA[Seebeck coefficient (μV·K -1 )]]> Power Factor Comparative Example 16 2700 13 45 Comparative Example 17 2200 18 72 Comparative Example 18 1600 22 75 Comparative Example 19 1210 26 78 Comparative Example 20 890 30 85 Comparative Example 21 800 32 88

[0157] The above description of the disclosed embodiments will enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein but is to be construed in the widest manner consistent with the principles and novel features disclosed herein.

Claims

1. A conductive polyaniline composite material, characterized in that: include: A carbon composite material and conductive polyaniline disposed on the surface of the carbon composite material; The carbon composite material comprises a carbon material and titanium dioxide fibers arranged on the surface of the carbon material; The titanium dioxide fiber comprises a titanium dioxide fiber body and a titanium nitride layer arranged on the titanium dioxide fiber body; The mass ratio of the conductive polyaniline to the carbon composite material is 1:(1-8); The carbon material is selected from one or more of carbon paper, graphene film, carbon nanotube film and porous carbon film; The titanium dioxide fiber has a diameter of 50-200 nm and a length of 100-500 nm.

2. The conductive polyaniline composite material according to claim 1, characterized in that: The length direction of the titanium dioxide fiber forms an angle with the surface of the carbon material.

3. The conductive polyaniline composite material according to claim 1, characterized in that: The thickness of the titanium nitride layer is 0.2-0.4 nm; The thickness of the conductive polyaniline is 30-100 nm.

4. The method for preparing a conductive polyaniline composite material according to any one of claims 1 to 3, wherein: include: The conductive polyaniline and the carbon composite material are mixed in a solution to obtain the conductive polyaniline composite material.

5. The method for preparing a conductive polyaniline composite material according to claim 4, characterized in that: The preparation method of the carbon composite material comprises: (1) Mixing carbon material and titanium source, growing titanium dioxide fibers on the surface of the carbon material by hydrothermal method to obtain titanium dioxide / carbon composite material; (2) The titanium dioxide / carbon composite material is subjected to nitriding treatment to obtain a carbon composite material.

6. The method for preparing a conductive polyaniline composite material according to claim 5, characterized in that: The molar ratio of the carbon material to the titanium source is 1:(0.01-0.1).

7. The method for preparing a conductive polyaniline composite material according to claim 5, characterized in that: The nitriding treatment specifically includes: heat-treating the titanium dioxide / carbon composite material in an ammonia atmosphere.

8. The method for preparing a conductive polyaniline composite material according to claim 7, wherein: The heat treatment conditions are: starting from room temperature, heating at a rate of 1-5°C·min -1 After the temperature reaches 1000~1200 K, keep it warm for 1~6h.

9. The method for preparing a conductive polyaniline composite material according to claim 4, characterized in that: The mass ratio of the conductive polyaniline to the carbon composite material is 1:(0.1-15).

10. The method for preparing a conductive polyaniline composite material according to any one of claims 4 to 9, characterized in that: The solution is a m-cresol solution.

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