Composite material, preparation method thereof and friction volt nano generator

Abstract

The invention provides a composite material, a preparation method thereof and a friction volt nano-generator, and the preparation method comprises the following steps: mixing a polymer monomer and a protonic acid solution to obtain a mixed modified solution, and placing a substrate in the mixed modified solution for reaction to obtain a mixed material; and mixing the mixed material with the metal oxide nanoparticles, adding an oxidizing agent to carry out polymerization reaction, taking out the composite substrate, and carrying out post-treatment to obtain the composite material. The polymer is modified through the synergistic effect of protonation and a metal-nitrogen coordination bond, synchronous improvement of material performance and stability is achieved, and the carrier concentration and conductivity of the polymer are effectively improved through the protonation effect of protonic acid; the transition metal nanoparticles and amido or imino in a polymer molecular chain form a firm coordinate bond, so that the interface bonding force and structural integrity between inorganic nanoparticles and an organic polymer matrix are greatly enhanced.

Description

Technical Field

[0001] This invention belongs to the technical field of triboelectric nanogenerators, and relates to a composite material, its preparation method, and a triboelectric nanogenerator. Background Technology

[0002] Tribovolt-nanogenerators (TVNGs), as an emerging technology for converting mechanical energy based on the built-in electric field at a semiconductor interface, demonstrate significant research value and development potential in the field of micro-energy because they can directly convert mechanical energy generated during the friction process into direct current signals, avoiding complex rectifier circuits. The performance and stability of TVNGs fundamentally depend on the efficiency of charge excitation, separation, and transport at their triboelectric interface, as well as the physical and chemical stability of the interface itself.

[0003] Currently, researchers have employed various interface contact modes to achieve high energy conversion efficiency. For example, while the sliding friction mode is beneficial for maintaining continuous charge excitation, the forced relative motion of the interface inevitably causes atomic-level interlocking and significant shear stress, leading to severe frictional wear, resulting in rapid degradation of output performance and a significant reduction in device lifespan. The contact-separation mode, although effective in mitigating interface wear and improving mechanical durability, typically limits the effective contact area and energy conversion time per unit cycle, making it difficult to improve output performance. Therefore, how to simultaneously achieve high output performance and high operational stability of TVNGs under any operating mode constitutes a long-standing technical challenge in this field.

[0004] Therefore, developing a material that can fundamentally and synergistically improve the output performance and long-term operational stability of TVNGs has become the key to overcoming existing technological bottlenecks and promoting their practical application. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention aims to provide a composite material, its preparation method, and a triboelectric nanogenerator. This invention achieves simultaneous improvement in material performance and stability through the synergistic effect of protonation and metal-nitrogen coordination bonds. The protonation effect of the protic acid effectively increases the carrier concentration and conductivity of the polymer. Simultaneously, the transition metal nanoparticles form strong coordination bonds with the amine or imine groups in the polymer molecular chain, greatly enhancing the interfacial bonding and structural integrity between the inorganic nanoparticles and the organic polymer matrix. This synergistic effect jointly promotes the efficient separation and rapid transport of triboelectric charges and significantly improves the mechanical stability of the device.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a method for preparing a composite material, the method comprising the following steps:

[0008] A polymer monomer and a protic acid solution are mixed to obtain a mixed modified solution, and the substrate is placed in the mixed modified solution to react and obtain a mixture.

[0009] The mixture is mixed with metal oxide nanoparticles, an oxidant is added to carry out a polymerization reaction, the composite substrate is removed, and the composite material is obtained after post-processing.

[0010] This invention employs a core approach of "protonation-coordination synergistic regulation." First, polymer monomers are protonated in a protic acid solution, increasing their conductivity from near-insulating to 6-8 S / m, significantly enhancing carrier concentration and conductivity. Then, metal oxide nanoparticles are introduced, forming stable coordination bonds between metal ions and the amino / imine groups on the polymer molecular chains, thereby strengthening interfacial bonding and the built-in electric field. This invention fully utilizes the enhancement of electrical properties from protonation and the strengthening of interfacial stability from coordination bonds to produce composite materials that simultaneously optimize charge separation efficiency and mechanical durability of the triboelectric layer without complex interfacial modifications or multilayer structures.

[0011] Preferably, the polymer monomer comprises any one or a combination of at least two of aniline, pyrrole, thiophene, or furan, with typical but non-limiting combinations including combinations of aniline and pyrrole, aniline and thiophene, or thiophene and furan.

[0012] Preferably, the protic acid includes any one or a combination of at least two of hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, oxalic acid, or citric acid. Typical but non-limiting combinations include combinations of hydrochloric acid and phosphoric acid, combinations of oxalic acid and citric acid, or combinations of trifluoroacetic acid and sulfuric acid, etc., with hydrochloric acid being the preferred choice.

[0013] Preferably, the molar concentration of the protic acid solution is 0.05 mol / L to 2 mol / L, for example: 0.05 mol / L, 0.1 mol / L, 0.5 mol / L, 1 mol / L or 2 mol / L, etc., and is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 0.5 mol / L to 1.5 mol / L.

[0014] Preferably, the molar concentration of the polymer monomer in the mixed modified solution is 0.5 mol / L to 1 mol / L, for example: 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L or 1 mol / L, etc., and is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0015] Preferably, the substrate comprises any one or a combination of at least two of polydimethylsiloxane, polyimide, carbon cloth, metal foil, fabric or glass sheet. Typical but non-limiting combinations include combinations of polydimethylsiloxane and polyimide, combinations of polyimide or carbon cloth, or combinations thereof.

[0016] Preferably, the area of ​​the substrate is 1 cm². 2 ~25cm 2 For example: 1cm 2 5cm 2 10cm 2 20cm 2 Or 25cm 2 The term "etc." is not limited to the listed values; it also applies to other unlisted values ​​within the range.

[0017] Preferably, the substrate is pretreated before being placed in the mixed modification solution.

[0018] Preferably, the pretreatment includes: first, ultrasonically treating the substrate sequentially in ethanol and deionized water for 3 to 5 minutes, for example: 3 minutes, 3.5 minutes, 4 minutes, 4.5 minutes, or 5 minutes, etc., not limited to the listed values, and other unlisted values ​​within this range are also applicable; then drying at 40°C to 60°C, for example: 40°C, 45°C, 50°C, 55°C, or 60°C, etc., not limited to the listed values, and other unlisted values ​​within this range are also applicable; finally, treating the dried substrate in an ultraviolet ozone cleaner for 10 to 20 minutes, for example: 10 minutes, 12 minutes, 15 minutes, 18 minutes, or 20 minutes, not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0019] Preferably, ultrasound is performed during the reaction.

[0020] Preferably, the reaction time is 0.5h to 2h, for example: 0.5h, 0.8h, 1h, 1.5h or 2h, etc., and is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0021] Preferably, the metal nanoparticles include any one or a combination of at least two of zinc oxide, titanium dioxide, ferric oxide, chromium oxide, nickel oxide, copper oxide, manganese dioxide, or cobalt tetroxide. Typical but non-limiting combinations include combinations of zinc oxide and titanium dioxide, ferric oxide and chromium oxide, or manganese dioxide and cobalt tetroxide, etc., with nickel oxide being the most preferred.

[0022] Preferably, based on the mass of the polymer monomer in the mixture being 100%, the amount of metal nanoparticles added is 2.5% to 15%, for example: 2.5%, 3%, 5%, 10% or 15%, etc., not limited to the listed values, and other unlisted values ​​within this range are also applicable, preferably 5% to 10%.

[0023] Preferably, the oxidant comprises an ammonium persulfate solution.

[0024] Preferably, the molar concentration of the ammonium persulfate solution is 0.5 mol / L to 1 mol / L, for example: 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L or 1 mol / L, etc., and is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0025] Preferably, ultrasound is performed during the polymerization reaction.

[0026] Preferably, the polymerization reaction time is 1h to 3h, for example: 1h, 1.5h, 2h, 2.5h or 3h, etc., and is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0027] Preferably, the post-processing includes sequentially washing the composite substrate with ethanol, washing it with deionized water, and drying it.

[0028] In a second aspect, the present invention provides a composite material prepared by the preparation method described in the first aspect.

[0029] Thirdly, the present invention provides a triboelectric nanogenerator comprising a triboelectric pair; the triboelectric pair comprising a composite material and an N-type semiconductor as described in the second aspect.

[0030] This invention overcomes the design limitations of traditional TVNGs, which struggle to balance performance and stability, and achieves a synergistic improvement in high output performance and long-term stable operation.

[0031] Preferably, the triboelectric nanogenerator is mechanically excited during use.

[0032] Preferably, the mechanical excitation pressure is 1N to 50N, for example: 1N, 5N, 10N, 20N or 50N, etc., and is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0033] Preferably, the frequency of the mechanical excitation is 0.1Hz to 5Hz, for example: 0.1Hz, 0.5Hz, 1Hz, 2Hz or 5Hz, etc., and is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0034] In this invention, the combined effect of key process parameters such as the type and doping amount of protonated acid and metal oxide, as well as mechanical excitation conditions, effectively achieves a significant increase in polymer carrier concentration and the construction of a stable coordination bond network, thereby simultaneously enhancing the charge separation and transport efficiency and mechanical bonding strength at the interface of the triboelectric nanogenerator. This method, by controlling the degree of protonation and coordination bonding, achieves both high output performance and operational stability of the device without the need for complex multilayer structures or additional interface modifications.

[0035] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] (1) This invention modifies polymers through the synergistic effect of protonation and metal-nitrogen coordination bonds, achieving simultaneous improvement in material properties and stability. The protonation effect of protic acids effectively increases the carrier concentration and conductivity of the polymer; at the same time, transition metal nanoparticles form strong coordination bonds with the amine or imine groups in the polymer molecular chain, greatly enhancing the interfacial bonding force and structural integrity between inorganic nanoparticles and the organic polymer matrix. This synergistic effect jointly promotes the efficient separation and rapid transport of triboelectric charges and significantly improves the mechanical stability of the device.

[0038] (2) The preparation process of the composite material described in this invention is simple and has good repeatability. The method is based on a mature in-situ polymerization process, with low raw material cost, simple preparation process, good repeatability, uniform and stable performance, and good repeatability and reliability. It provides a feasible technical path for the large-scale preparation of high-performance and high-stability TVNG.

[0039] (3) The triboelectric nanogenerator made using the composite material described in this invention can achieve a current of up to 12.5 μA and a voltage of 6.35 V under mild conditions, and its output performance can still maintain about 100% of the initial value after 50,000 continuous cycle tests and 6 months of natural storage. Attached Figure Description

[0040] Figure 1 This is a schematic diagram of the reaction for preparing composite materials provided in an embodiment of the present invention. Detailed Implementation

[0041] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention.

[0042] The "range" disclosed in this invention can be defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of the specific range. This type of range definition can include or exclude endpoints; any endpoint can be independently included or excluded, and they can be arbitrarily combined, meaning any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60~120 and 80~110 are listed for specific parameters, it is understood that ranges of 60~110 and 80~120 are also expected. Furthermore, if minimum range values ​​1 and 2 are listed, and maximum range values ​​3, 4, and 5 are also listed, then the following ranges are all expected: 1~3, 1~4, 1~5, 2~3, 2~4, and 2~5. In this invention, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0" and "5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is described as an integer ≥2, it is equivalent to listing integers such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For instance, when a parameter is described as an integer selected from "2~10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0043] In this invention, "a combination of at least two" refers to a quantity greater than or equal to two, unless otherwise specified. For example, "any combination of one or at least two" means one or more or more items. It can be understood that when referring to "a combination of at least two," it refers to any suitable combination of multiple items, that is, a combination of "at least two" items carried out in a manner that does not conflict with and enables the implementation of this invention.

[0044] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions.

[0045] The term "embodiment" as used in this invention means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment or implementation of the invention. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a mutually exclusive, independent, or alternative embodiment. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described in this invention can be combined with other embodiments.

[0046] Those skilled in the art will understand that the order in which the steps are written in the methods of the various embodiments does not imply a strict execution order. The detailed execution order of each step should be determined by its function and possible internal logic. Unless otherwise specified, all steps of the present invention may be performed sequentially or randomly, but are preferably performed sequentially. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the method may also include step (c), meaning that step (c) can be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0047] In this invention, open-ended technical features or solutions described using terms such as "comprising" do not exclude additional members beyond those listed unless otherwise specified. They can be considered as providing both closed-ended features or solutions comprised of the listed members and open-ended features or solutions that include additional members beyond the listed members. For example, A includes a1, a2, and a3. Unless otherwise specified, it may also include other members or exclude additional members. This can be considered as providing both technical features or solutions where "A is composed of a1, a2, and a3" or "A is selected from a1, a2, and a3," and technical features or solutions where "A includes not only a1, a2, and a3, but also other members."

[0048] In this invention, unless otherwise specified, the features or solutions corresponding to "and / or" include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. For example, "A and / or B" represents a group consisting of A, B, and "a combination of A and B". "Containing A and / or B" can mean "containing A, containing B, and containing A and B", or "containing A, containing B, or containing A and B", and can be appropriately understood according to the context.

[0049] In this invention, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on the quantity.

[0050] In this invention, "optional" means that something is optional, that is, it refers to any one of the two parallel solutions of "having" or "not having". If there are multiple "optional" options in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, then each "optional" option is independent.

[0051] In this invention, "room temperature" generally refers to 4℃~35℃, and can refer to 20℃±5℃. In some embodiments of this invention, room temperature refers to 20℃~30℃.

[0052] The substrates used in both the embodiments and comparative examples of this invention underwent the following pretreatment:

[0053] First, the substrate was ultrasonically treated in ethanol and deionized water for 4 minutes each, then dried at 50°C. Finally, the dried substrate was treated in an ultraviolet ozone cleaner for 15 minutes to obtain a clean substrate.

[0054] Example 1

[0055] This embodiment provides a composite material, and the reaction diagram for preparing the composite material is shown below. Figure 1 As shown, the composite material is prepared by the following method:

[0056] Aniline monomer was mixed with a 1 mol / L hydrochloric acid solution to obtain 100 mL of a mixed modified solution. The molar concentration of aniline monomer in the mixed modified solution was 0.5 mol / L. A clean piece of material with an area of ​​9 cm² was then prepared. 2 The carbon cloth was immersed in the mixed modification solution and ultrasonically treated for 1 hour to allow the solution to fully wet the substrate, thus obtaining the mixture.

[0057] 7.5% by weight of pre-prepared NiO nanoparticles were added to the mixture and ultrasonically dispersed for 30 min. Then, 0.5 mol / L ammonium persulfate solution was added as an oxidant to carry out the polymerization reaction for 2 h. After the reaction was completed, the substrate was removed and thoroughly washed with anhydrous ethanol and deionized water in sequence to remove unreacted monomers, oligomers and other by-products. The composite material was then dried in a vacuum oven at 60 °C for 6 h to obtain the composite material.

[0058] Example 2

[0059] This embodiment provides a composite material, and the reaction diagram for preparing the composite material is shown below. Figure 1 As shown, the composite material is prepared by the following method:

[0060] Aniline monomer was mixed with a 1 mol / L hydrochloric acid solution to obtain 100 mL of a mixed modified solution. The molar concentration of aniline monomer in the mixed modified solution was 0.5 mol / L. A clean piece of material with an area of ​​1 cm² was then prepared. 2The polydimethylsiloxane substrate was immersed in a mixed modification solution and ultrasonically treated for 0.5 h to allow the solution to fully wet the substrate, thus obtaining a mixture.

[0061] 5% by weight of pre-prepared NiO nanoparticles were added to the mixture and ultrasonically dispersed for 30 min. Then, 0.5 mol / L ammonium persulfate solution was added as an oxidant to carry out the polymerization reaction for 1 h. After the reaction was completed, the substrate was removed and thoroughly washed with anhydrous ethanol and deionized water in sequence to remove unreacted monomers, oligomers and other by-products. The composite material was then dried in a vacuum oven at 60 °C for 6 h to obtain the composite material.

[0062] Example 3

[0063] This embodiment provides a composite material, and the reaction diagram for preparing the composite material is shown below. Figure 1 As shown, the composite material is prepared by the following method:

[0064] A aniline monomer was mixed with a 1 mol / L hydrochloric acid solution to obtain 100 mL of a mixed modification solution. The molar concentration of the aniline monomer in the mixed modification solution was 1 mol / L. A clean piece of material with an area of ​​25 cm² was then used. 2 The polyimide substrate was immersed in the mixed modification solution and ultrasonically treated for 0.5 h to allow the solution to fully wet the substrate, thus obtaining the mixture.

[0065] 10% by weight of pre-prepared NiO nanoparticles of aniline monomer were added to the mixture and ultrasonically dispersed for 30 min. Then, 1 mol / L ammonium persulfate solution was added as an oxidant to carry out the polymerization reaction for 3 h. After the reaction was completed, the substrate was removed and thoroughly washed with anhydrous ethanol and deionized water in sequence to remove unreacted monomers, oligomers and other by-products. Then, the composite material was dried in a vacuum oven at 60 °C for 6 h to obtain the composite material.

[0066] Example 4

[0067] The only difference between this embodiment and Example 1 is that the molar concentration of hydrochloric acid is 0.1 mol / L; all other conditions and parameters are exactly the same as in Example 1.

[0068] Example 5

[0069] The only difference between this embodiment and Example 1 is that the molar concentration of hydrochloric acid is 2 mol / L; all other conditions and parameters are exactly the same as in Example 1.

[0070] Example 6

[0071] The only difference between this embodiment and Example 1 is that the amount of NiO added is 2.5% of the mass of the aniline monomer; all other conditions and parameters are exactly the same as in Example 1.

[0072] Example 7

[0073] The only difference between this embodiment and Example 1 is that the amount of NiO added is 15% of the mass of the aniline monomer; all other conditions and parameters are exactly the same as in Example 1.

[0074] Example 8

[0075] The only difference between this embodiment and Embodiment 1 is that hydrochloric acid is replaced with citric acid; all other conditions and parameters are exactly the same as in Embodiment 1.

[0076] Example 9

[0077] The only difference between this embodiment and Embodiment 1 is that hydrochloric acid is replaced with sulfuric acid; all other conditions and parameters are exactly the same as in Embodiment 1.

[0078] Example 10

[0079] The only difference between this embodiment and Embodiment 1 is that hydrochloric acid is replaced with phosphoric acid; all other conditions and parameters are exactly the same as in Embodiment 1.

[0080] Example 11

[0081] The only difference between this embodiment and Embodiment 1 is that hydrochloric acid is replaced with trifluoroacetic acid; all other conditions and parameters are exactly the same as in Embodiment 1.

[0082] Example 12

[0083] The only difference between this embodiment and Embodiment 1 is that hydrochloric acid is replaced with oxalic acid; all other conditions and parameters are exactly the same as in Embodiment 1.

[0084] Example 13

[0085] The only difference between this embodiment and Example 1 is that the amount of NiO added is 5% of the mass of the aniline monomer; all other conditions and parameters are exactly the same as in Example 1.

[0086] Example 14

[0087] The only difference between this embodiment and Example 1 is that the amount of NiO added is 10% of the mass of the aniline monomer; all other conditions and parameters are exactly the same as in Example 1.

[0088] Example 15

[0089] The only difference between this embodiment and Example 1 is that the amount of NiO added is 12.5% ​​of the mass of the aniline monomer; all other conditions and parameters are exactly the same as in Example 1.

[0090] Example 16

[0091] The only difference between this embodiment and Embodiment 1 is that NiO is replaced with Co3O4, while the other conditions and parameters are exactly the same as in Embodiment 1.

[0092] Example 17

[0093] The only difference between this embodiment and Embodiment 1 is that NiO is replaced with MnO2, while the other conditions and parameters are exactly the same as in Embodiment 1.

[0094] Example 18

[0095] The only difference between this embodiment and Embodiment 1 is that NiO is replaced with CuO; all other conditions and parameters are exactly the same as in Embodiment 1.

[0096] Comparative Example 1

[0097] The only difference between this comparative example and Example 1 is that hydrochloric acid is not added; all other conditions and parameters are exactly the same as in Example 1.

[0098] Comparative Example 2

[0099] The only difference between this comparative example and Example 1 is that nickel oxide is not added; all other conditions and parameters are exactly the same as in Example 1.

[0100] Application Example 1

[0101] This application example provides a triboelectric nanogenerator assembled from the composite material obtained in Example 1 and an N-type semiconductor. The device was tested using a linear motor tester and a 6514 electrometer at an 8N contact pressure and a 1Hz operating frequency.

[0102] Application Example 2

[0103] This application example provides a triboelectric nanogenerator assembled from the composite material obtained in Example 2 and an N-type semiconductor. The device was tested using a linear motor tester and a 6514 electrometer at a contact pressure of 1N and an operating frequency of 0.1Hz.

[0104] Application Example 3

[0105] This application example provides a triboelectric nanogenerator assembled from the composite material obtained in Example 3 and an N-type semiconductor. The device was tested using a linear motor tester and a 6514 electrometer at a contact pressure of 50 N and an operating frequency of 5 Hz.

[0106] Application Example 4

[0107] The only difference between this application example and application example 1 is that the composite material prepared in example 4 is used, while the other conditions and parameters are exactly the same as in application example 1.

[0108] Application Example 5

[0109] The only difference between this application example and application example 1 is that the composite material prepared in example 5 is used, while the other conditions and parameters are exactly the same as in application example 1.

[0110] Application Example 6

[0111] The only difference between this application example and application example 1 is that the composite material prepared in example 6 is used, while the other conditions and parameters are exactly the same as in application example 1.

[0112] Application Example 7

[0113] The only difference between this application example and application example 1 is that the composite material prepared in example 7 is used, while the other conditions and parameters are exactly the same as in application example 1.

[0114] Application Example 8

[0115] The only difference between this application example and application example 1 is that the composite material prepared in example 8 is used, while the other conditions and parameters are exactly the same as in application example 1.

[0116] Application Example 9

[0117] The only difference between this application example and application example 1 is that the composite material prepared in example 9 is used, while the other conditions and parameters are exactly the same as in application example 1.

[0118] Application Example 10

[0119] The only difference between this application example and application example 1 is that the composite material prepared in example 10 is used, while the other conditions and parameters are exactly the same as in application example 1.

[0120] Application Example 11

[0121] The only difference between this application example and application example 1 is that the composite material prepared in example 11 is used, while the other conditions and parameters are exactly the same as in application example 1.

[0122] Application Example 12

[0123] The only difference between this application example and application example 1 is that the composite material prepared in example 12 is used, while the other conditions and parameters are exactly the same as in application example 1.

[0124] Application Example 13

[0125] The only difference between this application example and application example 1 is that the composite material prepared in example 13 is used, while the other conditions and parameters are exactly the same as in application example 1.

[0126] Application Example 14

[0127] The only difference between this application example and application example 1 is that the composite material prepared in example 14 is used, while the other conditions and parameters are exactly the same as in application example 1.

[0128] Application Example 15

[0129] The only difference between this application example and application example 1 is that the composite material prepared in example 15 is used, while the other conditions and parameters are exactly the same as in application example 1.

[0130] Application Example 16

[0131] The only difference between this application example and application example 1 is that the composite material prepared in example 16 is used, while the other conditions and parameters are exactly the same as in application example 1.

[0132] Application Example 17

[0133] The only difference between this application example and application example 1 is that the composite material prepared in example 17 is used, while the other conditions and parameters are exactly the same as in application example 1.

[0134] Application Example 18

[0135] The only difference between this application example and application example 1 is that the composite material prepared in example 18 is used, while the other conditions and parameters are exactly the same as in application example 1.

[0136] Comparative Application Example 1

[0137] The only difference between this comparative application example and application example 1 is that the composite material prepared in comparative example 1 is used; all other conditions and parameters are exactly the same as in application example 1.

[0138] Comparative Application Example 2

[0139] The only difference between this comparative application example and application example 1 is that the composite material prepared in comparative example 2 is used; all other conditions and parameters are exactly the same as in application example 1.

[0140] The electrical conductivity of the composite materials prepared in the test examples and comparative examples was obtained, and the current and voltage of the triboelectric nanogenerators prepared in the application examples and comparative application examples were obtained. Five sets of parallel tests were performed for both the examples and comparative examples, and the average value of the test results was taken. "-" indicates that the measurement was not possible. The test results are shown in Table 1.

[0141] Table 1

[0142]

[0143] As can be seen from Table 1, based on application examples 1-3, the electrical conductivity of the composite material described in this invention can reach above 9.89 S / m, the current can reach above 9.16 μA, and the voltage can reach above 5.83 V. When the HCl concentration is 1 M and the NiO concentration is 7.5 wt%, the current and voltage reach their maximum values.

[0144] A comparison of Application Examples 1 and 4-5 shows that the molar concentration of the protonic acid used in the preparation of the composite material described in this invention affects its performance. Controlling the molar concentration of the protonic acid solution between 0.5 mol / L and 1.5 mol / L yields composite materials with better performance. If the molar concentration of the protonic acid solution is too low, protonation is insufficient, resulting in low conductivity of polyaniline (PANI) and limited output. If the molar concentration of the protonic acid solution is too high, excessive H+ will... + It may trigger side reactions, generating PANI isomers, which disrupt the conjugated structure of the molecular chain, leading to a decrease in conductivity and output performance.

[0145] A comparison of Application Example 1 and Application Examples 6-7 shows that the amount of metal nanoparticles added during the preparation of the composite material of the present invention affects its performance. When the amount of metal nanoparticles added is controlled at 5% to 10% of the mass of aniline monomer, the composite material has better performance. If the amount of metal nanoparticles added is too low, the coordination bond enhancement effect is not significant. If the amount of metal nanoparticles added is too high, the metal nanoparticles are prone to agglomeration, increasing interface defects, hindering charge transport, and leading to performance degradation.

[0146] A comparison of Application Example 1 and Comparative Application Example 1 shows that, during the preparation of the composite material described in this invention, in an acidic environment, nitrogen atoms on the polymer backbone of polyaniline capture protons (H atoms). + This causes the material to transform from an insulating state to a conductive emerald green imine salt form, thereby establishing an efficient charge transport path.

[0147] As can be seen from the comparison between Application Example 1 and Comparative Application Example 2, the addition of metal nanoparticles and the introduction of metal-nitrogen to form coordination bonds during the preparation of the composite material of the present invention can significantly improve the performance and stability of the material.

[0148] The optimal triboelectric nanogenerator prepared according to Example 1 of this invention was systematically tested:

[0149] (1) Effect of pressure: When tested in the pressure range of 1N to 50N, the current and voltage of the device increased with increasing pressure and then leveled off. Increased pressure enhanced interfacial contact, promoted the breaking and reconstruction of more chemical bonds, and thus excited more electron-hole pairs.

[0150] (2) Frequency effect: When tested in the frequency range of 0.1Hz to 5Hz, the current and voltage of the device increased significantly with increasing frequency. High-frequency mechanical excitation helps to improve charge separation and collection efficiency.

[0151] (3) Cyclic stability: After 50,000 continuous cycles under 8N pressure and 1Hz frequency, the output performance of the device did not show significant attenuation, the pulse waveform remained consistent, and the performance retention rate was almost 100%.

[0152] (4) Long-term stability: After storing the device in a natural environment (room temperature, fluctuating humidity) for 6 months, the performance was tested and the output performance retention rate reached almost 100%, showing excellent environmental stability.

[0153] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for preparing a composite material, characterized in that, The preparation method includes the following steps: A polymer monomer and a protic acid solution are mixed to obtain a mixed modified solution, and the substrate is placed in the mixed modified solution to react and obtain a mixture. The mixture is mixed with metal oxide nanoparticles, an oxidant is added to carry out a polymerization reaction, the composite substrate is removed, and the composite material is obtained after post-processing.

2. The preparation method according to claim 1, characterized in that, The polymer monomer includes any one or a combination of at least two of aniline, pyrrole, thiophene, or furan; Preferably, the protic acid includes any one or a combination of at least two of hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, oxalic acid, or citric acid, with hydrochloric acid being the most preferred. Preferably, the molar concentration of the protic acid solution is 0.1 mol / L to 2 mol / L, and more preferably 0.5 mol / L to 1.5 mol / L.

3. The preparation method according to claim 1 or 2, characterized in that, The molar concentration of the polymer monomer in the mixed modified solution is 0.5 mol / L to 1 mol / L.

4. The preparation method according to any one of claims 1-3, characterized in that, The substrate includes any one or a combination of at least two of the following: polydimethylsiloxane, polyimide, carbon cloth, metal foil, fabric or glass sheet; Preferably, the area of ​​the substrate is 1 cm². 2 ~25cm 2 ; Preferably, the substrate is pretreated before being placed in the mixed modification solution; Preferably, the pretreatment includes: first, placing the substrate in ethanol and deionized water in sequence for ultrasonic treatment for 3 min to 5 min respectively, then drying it at 40℃ to 60℃, and finally placing the dried substrate in an ultraviolet ozone cleaner for 10 min to 20 min.

5. The preparation method according to any one of claims 1-4, characterized in that, Ultrasound is applied during the reaction process; Preferably, the reaction time is 0.5h to 2h.

6. The preparation method according to any one of claims 1-5, characterized in that, The metal nanoparticles include any one or a combination of at least two of zinc oxide, titanium dioxide, ferric oxide, chromium oxide, nickel oxide, copper oxide, manganese dioxide, or cobalt tetroxide, preferably nickel oxide; Preferably, based on the mass of the polymer monomer in the mixture being 100%, the amount of metal nanoparticles added is 2.5% to 15%, more preferably 5% to 10%.

7. The preparation method according to any one of claims 1-6, characterized in that, The oxidant includes ammonium persulfate solution; Preferably, the molar concentration of the ammonium persulfate solution is 0.5 mol / L to 1 mol / L; Preferably, ultrasound is performed during the polymerization reaction; Preferably, the polymerization reaction takes 1 to 3 hours. Preferably, the post-processing includes sequentially washing the composite substrate with ethanol, washing it with deionized water, and drying it.

8. A composite material, characterized in that, The composite material is prepared by the preparation method according to any one of claims 1-7.

9. A triboelectric nanogenerator, characterized in that, The tribovolt nanogenerator comprises a tribological pair; The friction pair includes the composite material and N-type semiconductor as described in claim 8.

10. The triboelectric nanogenerator as described in claim 9, characterized in that, The tribovolt nanogenerator is mechanically excited during use; Preferably, the mechanical excitation pressure is 1N~50N; Preferably, the frequency of the mechanical excitation is 0.1Hz to 5Hz.

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