Concrete-based energy storage material as well as preparation method and application thereof

Abstract

The invention relates to an energy storage material for buildings, and particularly discloses a concrete-based energy storage material as well as a preparation method and application thereof. The concrete-based energy storage material comprises a concrete matrix, polyaniline and short carbon fibers, part of the short carbon fibers and polyaniline are connected through chemical bonds to form a compound, the concrete matrix is of a porous structure, and the compound is distributed inside and outside the porous structure. The concrete-based energy storage material provided by the invention has good mechanical properties and energy storage capacity.

Description

TECHNICAL FIELD

[0001] The present application relates to a building energy storage material, in particular to a concrete-based energy storage material and a preparation method and application thereof. BACKGROUND

[0002] With the development of sustainable energy and intelligent infrastructure, traditional building materials have been unable to meet the needs of structural and functional integration. In recent years, structural energy storage materials have gradually become a research hotspot, especially in intelligent buildings, self-powered systems and other applications. Multifunctional concrete materials with load-bearing and energy storage capabilities are particularly important.

[0003] However, there is still a lack of organic fusion of polyaniline and carbon fibers in concrete in the prior art, which realizes high capacitance performance while maintaining good structural performance. SUMMARY

[0004] In view of the defects or deficiencies in the prior art, the purpose of the present application is to provide a concrete-based energy storage material and a preparation method and application thereof. The concrete-based energy storage material has good mechanical properties and energy storage capacity.

[0005] The first aspect of the present application is to provide a concrete-based energy storage material, comprising:

[0006] Concrete matrix: having a porous structure;

[0007] Polyaniline;

[0008] Short carbon fibers;

[0009] Part of the short carbon fibers and polyaniline are connected by chemical bonds to form a composite; the composite is distributed inside and outside the porous structure.

[0010] In some embodiments, the short carbon fibers are carbon fibers including carboxyl groups obtained by oxidizing short carbon fiber raw materials; the carboxyl groups of the short carbon fibers are connected to the polyaniline by chemical bonds.

[0011] In some embodiments, the short carbon fibers also have carbon groups, and the short carbon fibers have hydrogen bonding forces with the polyaniline.

[0012] In some embodiments, the short carbon fiber raw material satisfies the following conditions:

[0013] (1) The length of the short carbon fiber raw material is 3mm-8mm;

[0014] (2) The fiber diameter of the short carbon fiber raw material is 5μm-12μm;

[0015] (3) the tensile strength of the short-cut carbon fiber raw material is 3.0 GPa to 5.0 GPa;

[0016] (4) the resistivity of the short-cut carbon fiber raw material is 1.0 x 10 -3 Ω·m to 1.6 x 10 -3 Ω·m.

[0017] A second aspect of the present application is to provide a preparation method of the concrete-based energy storage material of the first aspect, comprising the following preparation process:

[0018] oxidizing the short-cut carbon fiber raw material to obtain short-cut carbon fibers, and dispersing the short-cut carbon fibers into water to form a carbon fiber dispersion liquid;

[0019] adding an aniline monomer into the carbon fiber dispersion liquid and initiating an in-situ polymerization reaction to form a mixture containing a composite;

[0020] mixing the mixture with cement, fine aggregate, and water, and then stirring, molding, and curing to obtain the concrete-based energy storage material.

[0021] In some embodiments, the preparation method comprises the following mass percentage contents of each raw material:

[0022] short-cut carbon fiber raw material: 0.5% to 2%;

[0023] aniline monomer: 5% to 20%;

[0024] cement: 30% to 60%;

[0025] fine aggregate: 20% to 40%;

[0026] the rest is water;

[0027] Preferably, other additives are further included, and the mass percentage content of the other additives is 0 to 2%;

[0028] Preferably, the other additives include any one or more of dispersants and water-reducing agents.

[0029] In some embodiments, the oxidation treatment step of the short-cut carbon fiber raw material comprises:

[0030] immersing and treating the short-cut carbon fiber raw material in an acid solution, controlling the temperature to be 70°C to 100°C, and then filtering, washing, and drying after treatment for 2h to 9h to obtain short-cut carbon fibers;

[0031] Preferably, the acid solution comprises nitric acid and sulfuric acid in a molar ratio of 1:(0.5 to 1).

[0032] Preferably, the use amount ratio of the short-cut carbon fiber raw material to the acid solution is 20g to 40g / L.

[0033] In some embodiments, the in-situ polymerization reaction comprises: adding aniline monomer, initiator and organic protonic acid into the carbon fiber dispersion liquid, controlling the temperature to be 0-5°C, and reacting for 2-9 hours to obtain a mixture containing a composite;

[0034] Preferably, the mass of the initiator is 110%-130% of the mass of the aniline monomer;

[0035] Preferably, the initiator comprises any one of ferric chloride, potassium dichromate, and ammonium sulfate;

[0036] Preferably, the mass of the organic protonic acid is 50%-100% of the mass of the aniline monomer;

[0037] Preferably, the organic protonic acid comprises any one or more of p-toluenesulfonic acid, camphor sulfonic acid, and trifluoroacetic acid.

[0038] In some embodiments, the cement is a 42.5-grade Portland cement or a 52.5-grade Portland cement;

[0039] and / or;

[0040] The fine aggregate is a fine aggregate meeting the IS 383-2016 specification.

[0041] A third aspect of the present application is to provide a building material, which comprises the concrete-based energy storage material of the first aspect or the concrete-based energy storage material prepared by the preparation method of the second aspect.

[0042] The beneficial technical effects of the present application are:

[0043] The capacitance of the concrete-based energy storage material of the present application is 50 F / m 2 ~ 120 F / m 2 ; and the compressive strength is >40 Mpa. That is, the material provided by the present application has good mechanical properties and energy storage capacity, and the material has good application in intelligent roads, energy recovery floors, low-carbon building walls, etc. BRIEF DESCRIPTION OF DRAWINGS

[0044] Figure 1 The structural schematic diagram of the concrete-based energy storage material of some embodiments of the present application is shown;

[0045] Figure 2 The preparation process flowchart of the concrete-based energy storage material of some embodiments of the present application is shown.

[0046] The numbers in the drawings are as follows:

[0047] 100. Concrete-based energy storage material; 101. Concrete matrix; 102. Short-cut carbon fiber; 103. Polyaniline; 104. Composite material. Detailed Implementation

[0048] To better understand the technical solution of this application, the embodiments of this application will be described in detail below with reference to the accompanying drawings.

[0049] It should be understood that the described embodiments are merely some, not all, of the embodiments in this application. All other embodiments obtained by those skilled in the art based on the embodiments in this application without inventive effort are within the scope of protection of this application.

[0050] Unless otherwise expressly stated otherwise, all scopes referenced in this application include end values.

[0051] The terms “a” or “an” are used in this application to describe the elements and components described herein. This is done solely for convenience and to provide a general meaning for the scope of this application. Such a description should be understood to include one or at least one, and the singular includes the plural, unless clearly otherwise indicated. “Multiple” means two or more.

[0052] All figures in this application are approximate values, regardless of whether words such as "approximately" or "about" are used. The numerical values ​​may vary by 1%, 2%, 5%, 7%, 8%, 10%, etc. Whenever a figure with a value of N is disclosed, any figure with values ​​of N+ / -1%, N+ / -2%, N+ / -3%, N+ / -5%, N+ / -7%, N+ / -8%, or N+ / -10% will be explicitly disclosed, where "+ / -" indicates addition or subtraction, and the range from N-10% to N+10% is also disclosed.

[0053] Concrete-based energy storage materials refer to multifunctional materials with load-bearing and energy storage capabilities, including self-generating-energy-storage concrete and biomimetic self-generating-energy-storage concrete. The technical principle of self-generating-energy-storage concrete is as follows: by mimicking the layered structure of plant vascular bundles, a layered microstructure similar to plant vascular bundles is constructed, and flexible materials are filled into the interlayer pores, giving it the "blood vessel" function similar to plant vascular bundles, enabling efficient ion transport, thereby achieving power generation and energy storage. This material can be applied in various scenarios such as buildings, roads, remote base stations, and aircraft runways. For example, buildings can use this concrete wall panel to significantly reduce dependence on the external power grid, achieving "off-grid operation"; road surfaces can be designed as "zero-carbon" service areas capable of generating and storing electricity, allowing new energy vehicles to wirelessly charge while driving; unmanned base stations and environmental monitoring equipment in remote areas can operate stably relying on the self-generating characteristics of this concrete; even aircraft runways can utilize this material to achieve self-powered operation, promoting the development of urban air transportation.

[0054] However, there is currently a lack of concrete materials that can organically integrate polyaniline and carbon fiber into concrete, achieving high capacitance performance while maintaining good structural properties.

[0055] The first aspect of this application is to provide a concrete-based energy storage material, such as... Figure 1 The concrete-based energy storage material 100 includes a concrete matrix 101, polyaniline 103 and chopped carbon fibers 102. Some of the chopped carbon fibers 102 and polyaniline 103 are connected by chemical bonds to form a composite 104. The concrete matrix 101 has a porous structure, and the composite 104 is distributed inside and outside the porous structure.

[0056] The concrete matrix in this application refers to a main body formed of cement, fine aggregate and water, which has a porous structure.

[0057] In these embodiments, this application discloses that the porosity of the concrete matrix is ​​10% to 30%.

[0058] The porosity defined in this application includes conventional definitions in the materials science field, such as the percentage of pore volume in a material to the total volume of the material in its natural state. The measurement method used in this application includes conventional techniques in the field. The measurement method described in this application is as follows:

[0059] After drying, the concrete-based energy storage material was cut into square samples of approximately 20mm × 20mm. The thickness and actual side length were measured using a digital micrometer and vernier calipers, and its volume V was calculated. Its weight M0 was then measured. The square samples were then immersed in deionized water and soaked for 2 hours at room temperature and in air atmosphere. After soaking, the deionized water adsorbed on the surface was removed, and its weight Mt was measured. The porosity of the material satisfies the following mathematical relationship:

[0060] Porosity = (Mt - M0) / ρ × V × 100%;

[0061] In the above mathematical formula, ρ represents the density of deionized water, with units of mm. 3 / g, V is the volume of the square sample of the material, in mm. 3 The units for weights M0 and Mt are g. The weight measuring instrument is a 0.1% balance, and the models of the 0.1% balance, digital micrometer, and vernier caliper include, but are not limited to, any conventional models in this field.

[0062] In these embodiments, this application discloses a concrete matrix porosity of any one of 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, and 30%, or any one of the ranges of both of the above.

[0063] The short-cut carbon fiber in this application refers to carbon fiber obtained by pre-oxidation and carbonization treatment using polyacrylonitrile-based carbon fiber as raw material. This carbon fiber has good mechanical properties, which are described in detail in the following embodiments.

[0064] In this application, some short-cut carbon fibers are chemically bonded to polyaniline to form a composite. This composite is distributed both inside and outside the porous structure, forming a continuous electrode network within the pores of the concrete matrix. The polyaniline itself constitutes the first microelectrode, while the remaining short-cut carbon fibers adhere to the concrete matrix and form the second microelectrode. These two electrodes form a capacitor within the porous concrete structure, facilitating energy storage. The capacitance of this concrete-based energy storage material is 10 F / m. 2 ~100F / m 2 Meanwhile, the aforementioned composite material also possesses the mechanical properties of chopped carbon fibers, enabling the concrete-based energy storage material to also exhibit a certain compressive strength, such as >30 MPa. Therefore, the material provided in this application combines excellent mechanical properties with energy storage capacity. This material has promising applications in smart roads, energy recovery flooring, and low-carbon building facades.

[0065] In some embodiments, the chopped carbon fiber is carbon fiber containing carboxyl groups obtained by oxidizing chopped carbon fiber raw material; the carboxyl groups of the chopped carbon fiber are chemically bonded to the polyaniline.

[0066] In some embodiments, the chopped carbon fibers further comprise a carbon matrix, and the carbon matrix of the chopped carbon fibers has hydrogen bonding forces with the polyaniline.

[0067] In the composite formed by the short-cut carbon fibers and polyaniline of this application, there are chemical bonds between the short-cut carbon fibers and polyaniline, and there may also be hydrogen bonding or van der Waals forces, etc. These chemical bonds or forces are used to improve the bonding force between the short-cut carbon fibers and polyaniline, so that the composite has a branched structure and forms a conductive network.

[0068] In some embodiments, the above-mentioned chopped carbon fiber raw material meets the following conditions:

[0069] (1) The length of the above-mentioned short-cut carbon fiber raw material is 3mm to 8mm;

[0070] (2) The fiber diameter of the above-mentioned short-cut carbon fiber raw material is 5μm to 12μm;

[0071] (3) The tensile strength of the above-mentioned short-cut carbon fiber raw material is 3.0 GPa to 5.0 GPa;

[0072] (4) The resistivity of the above-mentioned short-cut carbon fiber raw material is 1.0 × 10⁻⁶. -3 Ω·m~1.6×10 -3 Ω·m.

[0073] The length of the short-cut carbon fiber raw material in this application refers to its average length. The specific measurement can be performed using any conventional measurement method in the field, such as direct measurement with vernier calipers.

[0074] In these embodiments, this application discloses that the length of the short-cut carbon fiber raw material is any one of 3mm, 3.5mm, 4mm, 4.5mm, 5mm, 5.5mm, 6mm, 6.5mm, 7mm, 7.5mm, 8mm or any one of the above two ranges.

[0075] The fiber diameter of the short-cut carbon fiber raw material in this application refers to its average fiber diameter, which can be measured using any conventional measurement method in the field, such as by scanning electron microscopy (SEM).

[0076] In these embodiments, this application discloses that the fiber diameter of the chopped carbon fiber raw material is any one of 5μm, 6μm, 7μm, 8μm, 9μm, 10μm, 11μm, 12μm or any one of the above two ranges.

[0077] The tensile strength of the short-cut carbon fiber raw material in this application refers to the material's resistance to tensile stress. It is the critical value for the material to transition from uniform plastic deformation to localized concentrated plastic deformation, reflecting the material's maximum load-bearing capacity. The calculation formula is: tensile strength = applied tensile force / cross-sectional area.

[0078] The method for determining the tensile strength of chopped carbon fiber raw materials in this application includes any conventional determination method in the art, and can be found in GB / T 1040 <Determination of Tensile Properties of Plastics>.

[0079] In these embodiments, this application discloses that the tensile strength of the chopped carbon fiber raw material is any one of 3.0 GPa, 4.0 GPa, 5.0 GPa, or any one of the above two ranges.

[0080] The resistivity of the short-cut carbon fiber raw material in this application is a physical quantity used to represent the resistance characteristics of a material. It is an indicator of the material's ability to resist the flow of electric current. It is an inherent property of the material and can be derived from the resistance formula R = ρ·L / S, where R represents resistance, L represents the length of the resistive material, S represents the cross-sectional area of ​​the resistive material, and ρ represents resistivity.

[0081] This application discloses in these embodiments that the resistivity of the chopped carbon fiber raw material is 1.0 × 10⁻⁶. -3 Ω·m, 1.1×10 -3 Ω·m, 1.2×10 -3 Ω·m, 1.3×10 -3 Ω·m, 1.4×10 -3 Ω·m, 1.5×10 -3 Ω·m, 1.6×10 -3 Any of Ω·m or any of the range values ​​of either of the above two.

[0082] The second aspect of this application is to provide a method for preparing the concrete-based energy storage material described in the first aspect, the method being as follows: Figure 2 The illustration includes the following preparation process:

[0083] S100: Short-cut carbon fiber raw material is oxidized to obtain short-cut carbon fiber, and the short-cut carbon fiber is dispersed in water to form a carbon fiber dispersion.

[0084] S200, Add aniline monomer to the above carbon fiber dispersion and initiate an in-situ polymerization reaction to form a mixture containing the composite;

[0085] S300. The above mixture is mixed with cement, fine aggregate and water, and then stirred, molded and cured to obtain concrete-based energy storage material.

[0086] The short-cut carbon fiber raw material of this application will be oxidized to give the short-cut carbon fiber a carboxyl group, which will facilitate the formation of a chemical bond with polyaniline in the future; at the same time, the short-cut carbon fiber may also have hydroxyl and carbonyl groups, any one or more of these hydroxyl and carbonyl groups will facilitate the formation of hydrogen bonding forces with polyaniline.

[0087] In some embodiments, the chopped carbon fibers are dispersed in water to form a carbon fiber dispersion. To promote the dispersion of carbon fibers in deionized water, this application also selects to add a surfactant, such as Tween 80, in some embodiments, wherein the mass of Tween 80 is about 5% of the mass of the carbon fibers.

[0088] In some embodiments, the above preparation method includes the following raw materials in the following mass percentage amounts:

[0089] Short-cut carbon fiber raw material: 0.5%–2%;

[0090] Aniline monomer: 5%–20%;

[0091] Cement: 30%–60%;

[0092] Fine aggregate: 20% ~ 40%;

[0093] The remainder is water.

[0094] In these embodiments, this application discloses that, based on the total mass of all raw materials, the mass percentage content of chopped carbon fiber raw material is 0.5% to 2%, the mass percentage content of aniline monomer is 5% to 20%, the mass percentage content of cement is 30% to 60%, and the mass percentage content of fine aggregate is 20% to 40%.

[0095] In these embodiments, this application discloses that, based on the total mass of all raw materials, the mass percentage content of chopped carbon fiber raw material is any one of 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, or any one of the ranges of both above.

[0096] In these embodiments, this application discloses that, based on the total mass of all raw materials, the mass percentage content of aniline monomer is any one of 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, or any one of the ranges of both above.

[0097] In these embodiments, this application discloses that, based on the total mass of all raw materials, the mass percentage content of cement is any one of 30%, 35%, 40%, 45%, 50%, 55%, 60%, or any one of the ranges of both of the above.

[0098] In these embodiments, this application discloses that, based on the total mass of all raw materials, the mass percentage content of fine aggregate is any one of 20%, 25%, 30%, 35%, 40%, or any one of the ranges of both of the above.

[0099] In some embodiments, other additives are also included, wherein the other additives are present in a mass percentage of 0 to 2%.

[0100] In some embodiments, the other additives mentioned above include one or more of dispersants and water-reducing agents.

[0101] The dispersant in this application refers to additives used to improve the fluidity and pumpability of concrete, such as polycarboxylate dispersants and lignin sulfonate dispersants.

[0102] The water-reducing agent in this application refers to an admixture used to reduce the amount of mixing water under the condition that the slump of concrete is basically the same, such as sodium methylene dimethyl dinaphthalene sulfonate polymer.

[0103] This application discloses in these embodiments that, based on the total mass of all raw materials, the mass percentage content of other additives is any one of 0, 0.1%, 0.5%, 1%, 1.5%, 2%, or any one of the ranges of both of the above.

[0104] In some embodiments, the oxidation treatment step of the above-mentioned chopped carbon fiber raw material includes:

[0105] Short-cut carbon fiber raw material is dispersed in an acid solution and impregnated at a temperature of 70℃~100℃ for 2h~9h. After filtration, washing and drying, short-cut carbon fiber is obtained.

[0106] This application discloses, in these embodiments, a controlled temperature of any one of 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, and 100°C, or any one of the ranges of both above. A processing time of any one of 2h, 3h, 4h, 5h, 6h, 7h, 8h, and 9h, or any one of the ranges of both above.

[0107] In some embodiments, the acid solution comprises nitric acid and sulfuric acid in a molar ratio of 1:(0.5 to 1).

[0108] The acid solution of this application is an acid solution obtained by diluting a certain amount of concentrated nitric acid (mass fraction of 68%) and concentrated sulfuric acid (mass fraction of 98%) with water. In the acid solution, the molar ratio of nitric acid to sulfuric acid is any one of 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1 or any one of the above two ranges.

[0109] In the above acidic solution, nitric acid is mainly used to oxidize the functional groups on the surface of carbon fibers, while sulfuric acid is mainly used to promote the reaction and also to reduce the decomposition of nitric acid.

[0110] In some embodiments, the ratio of the above-mentioned chopped carbon fiber raw material to acid solution is 20g to 40g / L.

[0111] In some embodiments of this application, the amount of chopped carbon fiber raw material and acid solution is controlled to generate carbon fibers having the above-mentioned functional groups.

[0112] In these embodiments, this application discloses that the ratio of the above-mentioned chopped carbon fiber raw material to acid solution is any one of 20 g / L, 25 g / L, 30 g / L, 35 g / L, 40 g / L, or any one of the above two ranges.

[0113] In some embodiments, the above-mentioned in-situ polymerization reaction includes: adding aniline monomer, initiator and organic protic acid to the above-mentioned carbon fiber dispersion, controlling the temperature at 0 to 5°C, and reacting for 2 to 9 hours to obtain a mixture containing the composite.

[0114] In these embodiments, this application discloses that the reaction temperature for in-situ polymerization is any one of 0°C, 1°C, 2°C, 3°C, 4°C, 5°C or any one of the above two ranges, and the reaction time is any one of 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or any one of the above two ranges.

[0115] In some embodiments, the mass of the initiator is 110% to 130% of the mass of the aniline monomer.

[0116] In these embodiments, this application discloses that the mass of the initiator is any one of 110%, 120%, or 130% of the mass of the aniline monomer, or any one of the ranges of both.

[0117] In some embodiments, the initiator includes any one of ferric chloride, potassium dichromate, and ammonium sulfate.

[0118] In some embodiments, the mass of the organic protic acid is 50% to 100% of the mass of the aniline monomer.

[0119] In these embodiments, this application discloses that the mass of the organic protic acid is any one of 50%, 60%, 70%, 80%, 90%, or 100% of the mass of the aniline monomer, or any one of the ranges of both of the above.

[0120] In some embodiments, the above-mentioned organic protic acid includes any one or more of p-toluenesulfonic acid, camphorsulfonic acid, and trifluoroacetic acid.

[0121] In some embodiments, the cement is 42.5 grade silicate cement or 52.5 grade silicate cement;

[0122] and / or;

[0123] The fine aggregates mentioned above are fine aggregates that conform to the IS 383-2016 standard.

[0124] The silicate cement of this application refers to a hydraulic cementitious material made from silicate cement clinker, an appropriate amount of gypsum, and specified admixtures. The silicate cement clinker is a hydraulic cementitious material with calcium silicate as the main mineral component, obtained by grinding raw materials mainly containing CaO, SiO2, Al2O3, and Fe2O3 into fine powder in an appropriate proportion and burning it until partially melted.

[0125] The 42.5 grade silicate cement and 52.5 grade silicate cement of this application meet the performance requirements shown in Table 1 below.

[0126] Table 1. List of properties of silicate cement

[0127]

[0128] Example 1-1

[0129] A method for preparing a concrete-based energy storage material is provided, wherein the raw materials for preparation are as follows:

[0130] Short-cut carbon fiber raw material: 1%;

[0131] Aniline monomer: 15%;

[0132] Cement (42.5 grade silicate): 55%;

[0133] Fine aggregate: 25%;

[0134] The remainder is water;

[0135] The properties of the short-cut carbon fiber raw material are shown in Table 2-1 below, and the cement is 52.5 grade silicate cement.

[0136] Table 2-1 List of Properties of Short-Cut Carbon Fiber Raw Materials

[0137]

[0138] The specific preparation process of this concrete-based energy storage material is as follows:

[0139] Short-cut carbon fiber raw material was dispersed in an acid solution for impregnation treatment. The acid solution was composed of nitric acid and sulfuric acid with a molar ratio of 1:0.7 and a hydrogen ion concentration of 11.5 mol / L. The ratio of short-cut carbon fiber raw material to acid solution was 30 g / L. The temperature was controlled at 75℃. After treatment for 4 hours, the raw material was filtered, washed with water and dried to obtain short-cut carbon fiber. The surface of the short-cut carbon fiber contained carboxyl functional groups.

[0140] The above-mentioned short-cut carbon fibers are dispersed in water to form a carbon fiber dispersion;

[0141] Aniline monomer, ammonium sulfate initiator, and toluenesulfonic acid were added to the above carbon fiber dispersion. The mass of ferric chloride was 110% of the mass of aniline monomer, and the mass of trifluoroacetic acid was 60% of the mass of aniline monomer. The temperature was controlled at 0°C, and the reaction was carried out for 5 hours to form a mixture containing the complex through in-situ polymerization.

[0142] The above mixture is mixed with cement, fine aggregate, and water, and then stirred, molded, and cured to obtain a concrete-based energy storage material.

[0143] Examples 1-2

[0144] A method for preparing a concrete-based energy storage material is provided. This method differs from that in Example 1-1 in that the properties of the chopped carbon fiber raw material are different, as illustrated in Table 2-2. All other aspects remain the same as in Example 1-1.

[0145] Table 2-2 List of Properties of Short-Cut Carbon Fiber Raw Materials

[0146]

[0147] Examples 1-3

[0148] A method for preparing a concrete-based energy storage material is provided. This method differs from that of Example 1-1 in that the properties of the chopped carbon fiber raw material are different, as illustrated in Table 2-3. All other aspects remain the same as in Example 1-1.

[0149] Table 2-3 List of properties of short-cut carbon fiber raw materials

[0150]

[0151] Examples 1-4

[0152] A method for preparing a concrete-based energy storage material is provided. This method differs from that of Example 1-1 in that the properties of the chopped carbon fiber raw material are different, as illustrated in Table 2-4. All other aspects remain the same as in Example 1-1.

[0153] Table 2-4 List of Properties of Short-Cut Carbon Fiber Raw Materials

[0154] Serial number Length (mm) Fiber diameter (pm) Tensile strength (GPa) Resistivity (Q-m) Examples 1-4 3.5 9 3.1 1.55

[0155] Example 2-1

[0156] A method for preparing a concrete-based energy storage material is provided. This method differs from that in Example 1-1 in that short-cut carbon fiber raw material is dispersed in an acid solution for impregnation treatment. The acid solution is a hydrogen ion concentration of 10 mol / L composed of nitric acid and sulfuric acid with a molar ratio of 1:0.5. The ratio of short-cut carbon fiber raw material to acid solution is 20 g / L. The temperature is controlled at 75°C. After treatment for 5 hours, the material is filtered, washed with water, and dried to obtain short-cut carbon fiber. The surface of the short-cut carbon fiber contains carboxyl functional groups.

[0157] The above-mentioned short-cut carbon fibers are dispersed in water to form a carbon fiber dispersion;

[0158] Aniline monomer, potassium dichromate initiator, and toluenesulfonic acid were added to the above carbon fiber dispersion. The mass of potassium dichromate was 110% of the mass of aniline monomer, and the mass of toluenesulfonic acid was 55% of the mass of aniline monomer. The temperature was controlled at 0°C, and the reaction was carried out for 5 hours to form a mixture containing the complex through in-situ polymerization.

[0159] The above mixture is mixed with cement, fine aggregate, and water, and then stirred, molded, and cured to obtain a concrete-based energy storage material.

[0160] Example 2-2

[0161] A method for preparing a concrete-based energy storage material is provided, which differs from that in Examples 1-1 in that...

[0162] Short-cut carbon fiber raw material was dispersed in an acid solution for impregnation treatment. The acid solution was composed of nitric acid and sulfuric acid in a molar ratio of 1:1 with a hydrogen ion concentration of 14 mol / L. The ratio of short-cut carbon fiber raw material to acid solution was 40 g / L. The temperature was controlled at 80℃. After treatment for 3 hours, the raw material was filtered, washed with water, and dried to obtain short-cut carbon fiber. The surface of the short-cut carbon fiber contained carboxyl functional groups.

[0163] The above-mentioned short-cut carbon fibers are dispersed in water to form a carbon fiber dispersion;

[0164] Aniline monomer, ammonium sulfate initiator, and toluenesulfonic acid were added to the above carbon fiber dispersion, wherein the mass of ammonium sulfate was 130% of the mass of aniline monomer, the mass of toluenesulfonic acid was 95% of the mass of aniline monomer, the temperature was controlled at 0℃, and the reaction was carried out for 5 hours to form a mixture containing the complex through in-situ polymerization.

[0165] The above mixture is mixed with cement, fine aggregate, and water, and then stirred, molded, and cured to obtain a concrete-based energy storage material.

[0166] Example 3-1

[0167] A method for preparing a concrete-based energy storage material is provided. This method differs from that in Example 1-1 in that the proportions of the raw materials are different, as detailed below:

[0168] Short-cut carbon fiber raw material: 2%;

[0169] Aniline monomer: 15%;

[0170] Cement: 55%;

[0171] Fine aggregate: 25%;

[0172] The remainder is water.

[0173] Example 3-2

[0174] A method for preparing a concrete-based energy storage material is provided. This method differs from that in Example 1-1 in that the proportions of the raw materials are different, as detailed below:

[0175] Short-cut carbon fiber raw material: 0.5%;

[0176] Aniline monomer: 15%;

[0177] Cement: 55%;

[0178] Fine aggregate: 25%;

[0179] The remainder is water.

[0180] Example 3-3

[0181] A method for preparing a concrete-based energy storage material is provided. This method differs from that in Example 1-1 in that the proportions of the raw materials are different, as detailed below:

[0182] Short-cut carbon fiber raw material: 2.5%;

[0183] Aniline monomer: 15%;

[0184] Cement: 55%;

[0185] Fine aggregate: 25%;

[0186] The remainder is water.

[0187] Example 4-1

[0188] A method for preparing a concrete-based energy storage material is provided. This method differs from that in Example 1-1 in that the proportions of the raw materials are different, as detailed below:

[0189] Short-cut carbon fiber raw material: 1%;

[0190] Aniline monomer: 15%;

[0191] Cement: 55%;

[0192] Fine aggregate: 25%;

[0193] Graphene: 0.5%; wherein, the graphene is a commercially available product in this field, and the manufacturer and model can be any type.

[0194] The remainder is water.

[0195] Comparative Example 1

[0196] A concrete composite material is provided, which differs from that of Examples 1-1 in that it does not contain chopped carbon fibers, and the raw material composition is as follows:

[0197] Aniline monomer: 15%;

[0198] Cement: 55%;

[0199] Fine aggregate: 25%;

[0200] The remainder is water.

[0201] In all other respects, it remains the same as in Example 1-1.

[0202] Comparative Example 2

[0203] A concrete composite material is provided, which differs from that of Example 1-1 in that the short-cut carbon fibers are added directly without oxidation treatment, while other aspects remain the same as those of Example 1-1.

[0204] Performance testing

[0205] (1) Test the capacitance of the material at 25℃:

[0206] Cyclic voltammetry (CV) was used.

[0207] (2) Test the compressive strength of the material at 25℃:

[0208] Refer to GB / T 50081-2019 "Test Methods for Physical and Mechanical Properties of Concrete".

[0209] (3) Test the porosity of the material:

[0210] Conventional testing methods in this field, such as those used in the following embodiments, employ indirect testing.

[0211] The test results are shown in Table 3:

[0212] Table 3. Performance Test List of Examples and Comparative Examples

[0213] Serial number Capacitance value (F / m 2 ) Compressive strength (Mpa) Porosity (%) Example 1-1 90 45 14 Example 1-2 75 52 17 Example 1-3 110 57 13 Example 2-1 65 46 16 Example 2-2 100 48 18 Example 2-3 120 55 16 Example 3-1 80 45 18 Example 3-2 60 42 16 Example 3-3 70 40 21 Example 4-1 100 55 13 Comparative Example 1 35 42 12 Comparative Example 2 55 43 12

[0214] As shown in the above list, the capacitance of the concrete-based energy storage material in this application is 50 F / m. 2 ~120F / m 2 The compressive strength is >40 MPa. In other words, the material provided in this application possesses both excellent mechanical properties and energy storage capacity, making it well-suited for applications in smart roads, energy-recovery flooring, and low-carbon building facades.

[0215] The above description of the embodiments is only for the purpose of helping to understand the method and core idea of ​​this application; at the same time, for those skilled in the art, there will be changes in the specific implementation and application scope based on the idea of ​​this application. Therefore, the content of this specification should not be construed as a limitation of this application.

[0216] Certain terms are used in the specification and claims to refer to specific components. Those skilled in the art will understand that hardware manufacturers may use different names to refer to the same component. This specification and claims do not distinguish components based on differences in name, but rather on differences in function. The terms "comprising" and "including" used throughout the specification and claims are open-ended and should be interpreted as "comprising / including but not limited to". "Approximately" means that within an acceptable margin of error, those skilled in the art can solve the technical problem and substantially achieve the technical effect within a certain margin of error. The following descriptions in the specification are preferred embodiments for carrying out this application; however, these descriptions are for the purpose of illustrating the general principles of this application and are not intended to limit the scope of this application. The scope of protection of this application shall be determined by the appended claims.

[0217] It should also be noted that the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a product or system comprising a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a product or system. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the product or system that includes said element.

[0218] It should be understood that the term "and / or" used in this article is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, and B existing alone. Additionally, the character " / " in this article generally indicates that the preceding and following related objects have an "or" relationship.

[0219] The above description is merely a preferred embodiment of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A concrete-based energy storage material, characterized in that: include: Concrete matrix: Porous structure; Polyaniline; Short-cut carbon fibers; Some of the chopped carbon fibers are chemically bonded to polyaniline to form a composite; The complex is distributed both inside and outside the porous structure.

2. The concrete-based energy storage material according to claim 1, characterized in that: The chopped carbon fiber is obtained by oxidizing chopped carbon fiber raw material to obtain carbon fiber containing carboxyl groups; the carboxyl groups of the chopped carbon fiber are connected to the polyaniline by chemical bonds; Preferably, the chopped carbon fibers further comprise a carbon matrix, and the carbon matrix of the chopped carbon fibers has hydrogen bonding forces with the polyaniline.

3. The concrete-based energy storage material according to any one of claims 1 to 2, characterized in that: The porosity of the concrete matrix is ​​10% to 30%.

4. The concrete-based energy storage material according to claim 2, characterized in that: The short-cut carbon fiber raw material meets the following conditions: (1) The length of the short-cut carbon fiber raw material is 3mm to 8mm; (2) The fiber diameter of the short-cut carbon fiber raw material is 5μm to 12μm; (3) The tensile strength of the chopped carbon fiber raw material is 3.0 GPa to 5.0 GPa; (4) The resistivity of the chopped carbon fiber raw material is 1.0 × 10⁻⁶. -3 Ω·m~1.6×10 -3 Ω·m.

5. A method for preparing the concrete-based energy storage material according to claim 1, characterized in that: The preparation process includes the following: Short-cut carbon fiber raw material is oxidized to obtain short-cut carbon fiber, and the short-cut carbon fiber is dispersed in water to form a carbon fiber dispersion. Aniline monomer is added to the carbon fiber dispersion and an in-situ polymerization reaction is initiated to form a mixture containing the composite. The mixture is mixed with cement, fine aggregate, and water, and then stirred, molded, and cured to obtain a concrete-based energy storage material.

6. The preparation method according to claim 5, characterized in that: The preparation method includes the following raw materials in the following mass percentages: Short-cut carbon fiber raw material: 0.5%–2%; Aniline monomer: 5%–20%; Cement: 30%–60%; Fine aggregate: 20% ~ 40%; The remainder is water; Preferably, it includes other additives, wherein the mass percentage of said other additives is 0-2%; Preferably, the other additives include one or more of dispersants and water-reducing agents; Preferably, it includes other conductive agents, wherein the mass percentage content of the other conductive agents is 0 to 2%; Preferably, the other conductive agent includes one or more of graphene or carbon black.

7. The preparation method according to any one of claims 5 to 6, characterized in that: The oxidation treatment step of the short-cut carbon fiber raw material includes: Short-cut carbon fiber raw material is dispersed in an acid solution and impregnated at a temperature of 70℃~100℃ for 2h~9h. After filtration, washing and drying, short-cut carbon fiber is obtained. Preferably, the acid solution comprises nitric acid and sulfuric acid in a molar ratio of 1:(0.5-1); Preferably, the ratio of the chopped carbon fiber raw material to the acid solution is 20g to 40g / L.

8. The preparation method according to any one of claims 5 to 6, characterized in that: The in-situ polymerization reaction includes: adding aniline monomer, initiator and organic protic acid to the carbon fiber dispersion, controlling the temperature at 0-5℃, and reacting for 2-9 hours to obtain a mixture containing the complex; Preferably, the mass of the initiator is 110% to 130% of the mass of the aniline monomer; Preferably, the initiator includes any one of ferric chloride, potassium dichromate, and ammonium sulfate; Preferably, the mass of the organic protic acid is 50% to 100% of the mass of the aniline monomer; Preferably, the organic protic acid includes one or more of p-toluenesulfonic acid, camphorsulfonic acid, and trifluoroacetic acid.

9. The preparation method according to any one of claims 5 to 6, characterized in that: The cement is either grade 42.5 silicate cement or grade 52.5 silicate cement; and / or; The fine aggregate is fine aggregate conforming to the IS 383-2016 standard.

10. A building material, characterized in that: The concrete-based energy storage material includes any one of claims 1 to 4 or any one of claims 5 to 9.

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