Cement-based thermal insulation and energy storage integrated building material and preparation method thereof

Abstract

The invention belongs to the technical field of building materials, and discloses a cement-based thermal insulation and energy storage integrated building material and a preparation method thereof.The cement-based thermal insulation and energy storage integrated building material comprises an interface functional layer and an energy storage thermal insulation layer, the interface functional layer is attached to the surface of a cement-based wall / board and has the electrode material function of a capacitor, the thickness of the interface functional layer is 2-3 mm, and the thickness of the energy storage thermal insulation layer is 2-3 mm; the energy storage and heat preservation layer is located on the interface function layer, has good heat preservation and heat insulation capacity and also has an energy storage function, and the thickness of the energy storage and heat preservation layer is 80-100 mm; through material component design of the interface function layer and the energy storage heat preservation layer, the building-structure supercapacitor is formed and has the energy storage function, the interface function layer serves as an electrode function, the energy storage heat preservation layer serves as an electrolyte function, a building material integrating heat preservation and energy storage is formed, the building material can be combined with a building bearing structure, and the energy storage function is achieved. New energy electric power such as light energy and wind energy generated by the building is stored, and daily electricity utilization of the building is met through electric power release.

Description

Technical Field

[0001] The present invention belongs to the technical field of building materials, and in particular relates to a cement-based thermal insulation and energy storage integrated building material and a preparation method thereof. Background Art

[0002] Photovoltaic power generation technology has been widely applied to the walls and roofs of buildings. Building structures have enormous exterior surfaces and inherent volumes. Leveraging this vast surface area for power generation not only generates more electricity through external photovoltaic power generation, but also allows for the storage and regulation of electricity within the building's volume, effectively reducing daily energy consumption and contributing to the realization of low-carbon / zero-carbon architecture. Currently, electricity storage primarily utilizes chemical batteries, but these batteries are expensive, require specialized design for their placement, and pose a risk of leakage and pollution. Storing and regulating generated electricity is a major technical challenge hindering the development of photovoltaic power generation in buildings.

[0003] The design of building exterior wall insulation is a crucial measure for reducing energy consumption and improving housing comfort. These insulation layers are often made of lightweight, porous inorganic materials such as rock wool, rock slabs, and foam boards. These porous structures and the low thermal conductivity of these inorganic materials provide thermal insulation for building exterior walls. However, without increasing the space required, utilizing the internal volume and composition of building materials to store energy, enabling the storage and regulation of renewable energy, and thus enabling building walls to integrate thermal insulation and energy storage, is a pressing issue. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides a cement-based integrated thermal insulation and energy storage building material and a preparation method thereof. In response to the development needs of smart cities for multifunctional and green buildings, the thermal insulation layer material of the building exterior wall is designed in a targeted manner, and an interface functional layer is added between the cement-based wall and the thermal insulation layer material to give the building wall the functions of energy storage and thermal insulation.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is: a cement-based thermal insulation and energy storage integrated building material, including an interface functional layer and an energy storage and thermal insulation layer. The interface functional layer is attached to the surface of the cement-based wall / board and has the function of a capacitor electrode material; the thickness of the interface functional layer is 2-3 mm, and the key performance indicators of the interface functional layer are: bonding strength ≥ 1 MPa; area specific capacitance ≥ 500 F / m 2 The energy storage insulation layer is located above the interface functional layer and has good thermal insulation capabilities and electrolyte functions. The thickness of the energy storage insulation layer is 80~100mm. The key performance indicators of the energy storage insulation layer are: volume density 300~350kg / m 3, thermal conductivity 0.07~0.08W / m·K, ionic conductivity ≥0.03mS / cm; resistivity ≤50Ω·cm.

[0006] The interface functional layer and the energy storage insulation layer are constructed based on the building cement-based wall / building board. The cement-based wall / board is a load-bearing structural layer of a multifunctional building material with a load-bearing function. A vertical partition is provided on the surface of the cement-based wall / board. The vertical partition divides the surface of the cement-based wall / board into squares. The space inside the square is used to fill the interface functional layer and the energy storage insulation layer material. Each square is an energy storage unit, and the size of the energy storage unit can be designed according to the building form and energy storage application scenario. The vertical partition can be made of cement-based materials or other inorganic materials. T-shaped metal embedded parts and L-shaped metal embedded parts need to be embedded in the vertical partition. The vertical partition is anchored by the T-shaped metal embedded parts and the L-shaped metal embedded parts, and the energy transmission between the internal energy storage unit and the external control device is carried out.

[0007] The interface functional layer includes carbon fiber mesh and composite slurry. The carbon fiber mesh is cut according to the surface area of ​​the cement-based wall / board. The raw material components of the composite slurry are as follows: 40-50 parts of cementitious material; 35-40 parts of porous ceramsite; 3-4 parts of graphene nanosheets; and 150-200 parts of dispersion liquid. The cementitious material is 42.5 grade ordinary Portland cement; The porous ceramsite is shale ceramsite with a particle size of ≤2mm and a bulk density of ≤0.85g / cm 3 ; The graphene nanosheet particles should have a particle size D50 of ≤3 μm, a thickness of 5-50 nm, and a specific surface area of ​​≥600 m 2 / g, thermal conductivity ≥3500w / m·K, electrical conductivity ≥100S / m; The dispersion is a polycarboxylic acid solution with a solid content of ≥35%; The carbon fiber mesh cloth should have a thickness of ≤200 μm and a mesh size of 0.3-0.8 mm.

[0008] The raw material components of the energy storage and thermal insulation layer are calculated by weight as follows: 70-75 parts of red mud, 20 parts of metakaolin, 5 parts of sodium silicate, 3-4 parts of aluminum powder, 3-5 parts of foaming stabilizer; 1-2 parts of potassium hydroxide, 1-2 parts of potassium chloride, 2-5 parts of iron oxide powder, and 55-60 parts of mixing water.

[0009] The red mud is the original red mud discharged from the Bayer process electrolytic aluminum industry; the metakaolin is a powder obtained by calcining kaolin powder at 750-850°C; The modulus of the sodium silicate is 1.2-1.5; the aluminum powder is a foaming aluminum powder with a mesh size of 100-150 and an active aluminum content of ≥98%; The foaming stabilizer is prepared by compounding polycarboxylic acid mother liquor with polyacrylamide, sodium dodecylbenzenesulfonate, and polyethylene glycol type alkyl acid polyoxyethylene ether, with the mass ratio of the three being 1: (0.4-0.45): (0.2-0.3). The solid content of the compounded foaming stabilizer is ≥40%.

[0010] A method for preparing a cement-based thermal insulation and energy storage integrated building material, comprising the construction of an interface functional layer and the pouring of an energy storage and thermal insulation layer; The raw material processing and construction process of the interface functional layer includes the following steps: (1) preparation of graphene nanosheet dispersion: adding graphene nanosheets to 50 times the weight of the dispersion, ultrasonically dispersing for 2 hours, and obtaining the graphene nanosheet dispersion; (2) conductive aggregate treatment: using porous ceramsite as a carrier, immersing the ceramsite in 4 times the weight of the graphene nanosheet dispersion, and then transferring the dispersion to a stainless steel reactor, and performing hydrothermal treatment at 160°C for 12 hours; after the treatment, the ceramsite is filtered and dried in a 60°C forced air drying oven for 2 hours to obtain a conductive aggregate; (3) composite slurry preparation: adding the conductive aggregate to the remaining weight of the ceramsite; 1 part of graphene dispersion, half of the weight of mixing water is wetted, put into a mixer, start stirring at a speed of 100 r / min, and slowly add the cementitious material during the stirring process; after the cementitious material is added, continue stirring for 3 minutes; add the remaining half of the mixing water, and stir on the mixer at a speed of 300 r / min for 3 minutes to obtain a composite slurry; (4) Corrosion treatment and cutting of carbon fiber mesh cloth: The cut carbon fiber mesh is arranged in a mixture of 1 mol / L concentrated HNO3 and 2 mol / L concentrated H2SO4, and heat-treated at 60℃ for 2 hours; after treatment, it is repeatedly rinsed with deionized water until neutral. Cut according to the inner surface size of the frame composed of wall / board and vertical partition board; (5) Construction of interface functional layer: The prepared composite slurry is applied to the inner surface of the frame composed of wall / board and vertical partition board, and the coating thickness is controlled to be 2~3 mm, and then the cut carbon fiber mesh cloth is glued on.

[0011] The raw material processing and pouring process of the energy storage insulation layer includes the following steps: (1) drying: drying the original red mud at a temperature of 80°C for 0.5 to 1 hour, and controlling the moisture content of the material after drying to be less than 2%; (2) grinding: grinding and dispersing the dried red mud using a ball mill, and grinding for 5 to 10 minutes, and controlling the particle size of the material after grinding to be 45 μm with a sieve residue of ≤3%; (3) mixing the ingredients: weighing red mud, metakaolin, and aluminum powder in proportion, adding 70% mixing water, mixing them, and Stirring, mixing on a mixer at a speed of 300 rpm / min for 5 minutes to form a slurry mixture; then, sodium silicate, foaming stabilizer, potassium hydroxide, potassium chloride, iron oxide powder and 30% mixing water are mixed and added to the slurry, and stirring is continued at a speed of 150-200 rpm / min for 3 minutes to form a foaming slurry; (4) Pouring foaming: Pour the stirred slurry into the grid space of the cement-based wall / board where the interface functional layer has been constructed, and the mass of the poured slurry is 30-35 kg / m 2 .

[0012] Basic principles of the present invention: This cement-based building material combines energy storage and insulation. T-shaped and L-shaped metal pre-embedded components are embedded in vertical partitions on the exterior surface of the cement-based wall / panel to transmit energy between the external and internal energy storage units. These components also act as anchors for structural stress, improving the overall reliability of the cement-based wall / panel. The interface functional layer, a functional component attached between the cement-based wall / panel and the insulation material, possesses a high specific surface area, high electrical conductivity, excellent mechanical properties, and electrochemical stability, meeting the energy storage requirements of the building material. The energy storage insulation layer is a filling component above the interface functional layer. It has the characteristics of lightness and porosity. While reducing the overall weight of the building materials, its low heat transfer coefficient can provide good thermal insulation capabilities, and it acts as a filler and thermal insulation layer in terms of thermal insulation function. At the same time, the porous structure can store ions and provide channels for ion transmission. In terms of energy storage function, it acts as an electrolyte component of the supercapacitor, meeting the energy storage needs of the building materials. The thermal insulation function is mainly achieved through the low thermal conductivity of the energy storage insulation layer, and the energy storage function realizes electrical energy storage through the supercapacitor formed by the combination of the interface functional layer and the energy storage insulation layer.

[0013] The electrodes of supercapacitors store charge in the form of electrostatic adsorption. Carbon materials such as graphite, carbon fiber, carbon nanotubes, and graphene have long-term cyclic stability and are commonly used in the preparation of electrode materials. The present invention uses multilayer graphene oxide nanosheets as the electrode active material. Graphene is a nanomaterial with excellent performance. Its particles are small and its specific surface area is large, which leads to small size effect, surface effect, quantum effect, and interface effect. The electron mobility of graphene exceeds 15,000 cm 2 / (V•S), while the resistivity is only about 10 -6 Ω·cm, with low resistivity; Graphene also possesses excellent thermal conductivity, reaching up to 5300 W / m·K, making it an ideal electrode active material. This invention utilizes graphene nanosheets with a thickness of 5nm to 50nm, whose performance more closely resembles that of single-layer graphene oxide. To overcome graphene nanosheet agglomeration and improve their electrical properties, the invention utilizes a polycarboxylic acid solution for dispersion. Through the adsorption of carboxylic acid molecules and steric hindrance, the hydrophobic graphene nanosheets are rendered hydrophilic. This improves the compatibility and dispersibility of the graphene nanosheets with cement-based materials, making them suitable as electrode active materials in cement-based composites.

[0014] To increase the effective density of the electrode material in the interface functional layer, the present invention utilizes porous ceramsite as a carrier for graphene nanosheets. Porous ceramsite is a lightweight, high-strength, porous functional material widely used in construction, environmental protection, agriculture, and other fields. Its low density and porous structure provide excellent adsorption properties and is also commonly used as aggregate for lightweight, insulating concrete. The present invention utilizes a vacuum hydrothermal method to prepare the conductive aggregate, which is then loaded with graphene nanosheets within the porous interior of the aggregate. This increases the graphene nanosheet content at the electrode transition interface and improves the electrical performance of the electrode material.

[0015] The present invention utilizes a corroded carbon fiber mesh as a current collector for loading active materials. Carbon fiber is an excellent electrode current collector material, boasting excellent mechanical properties, chemical / electrochemical stability, and good electrical conductivity. However, due to its low specific surface area and surface activity, the electrochemical storage capacity of carbon fiber electrodes is very low. The carbon fiber mesh requires a pre-corrosion treatment to reduce surface defects and improve its loading capacity for conductive media.

[0016] Red mud is a byproduct of the alumina production process. my country's electrolytic aluminum industry is massive, with annual emissions exceeding 100 million tons. This massive stockpile not only occupies land but also severely impacts the environment and the sustainable development of the industry. Red mud is a highly alkaline solid waste, primarily composed of Si, Al, Fe, Ca, Na, and K. Its pH generally ranges from 10 to 13, with an Al₂O₃ + Fe₂O₃ content exceeding 50%. Its primary mineral composition includes hematite, cancrinite, calcite, boehmite, and gibbsite. Red mud has a relatively loose microstructure, primarily composed of irregularly shaped aggregates of red mud particles. Raw red mud aggregates possess a rich pore structure with pore diameters ranging from approximately 0.2 to 0.5 μm. These particles possess a large surface area, high water absorption, and strong water retention, providing storage and transport pathways for Fe and Al ions, making them an ideal matrix material for solid electrolytes. Combining chemical foaming technology can further improve its porosity and pore structure, so that the internal material can maintain a porous and stable physical structure. Metakaolin is the product of kaolin activated at high temperature. It is a highly active aluminum silicate raw material. Under alkaline conditions, it can form a silicon aluminum salt cementing material with an amorphous to semi-crystalline three-dimensional structure through polymerization. The present invention uses sodium silicate as an active stimulant and metakaolin as a polymerization agent to achieve a certain mechanical strength of the internal filling material. Aluminum powder is used as a foaming agent to achieve foaming of the internal filling material. When aluminum powder reacts with water and alkaline substances, it releases hydrogen and can form pores inside the material. It is a good chemical foaming agent. At the same time, the addition of aluminum powder increases the concentration of iron and aluminum ions in the internal filling component, thereby improving the conductivity of the internal filling material. A homemade foaming stabilizer is used to improve the stability of the foamed structure. The foaming stabilizer is compounded by polycarboxylic acid mother liquor with polyacrylamide, sodium dodecylbenzenesulfonate, and polyethylene glycol type alkyl acid polyoxyethylene ether. As a macromolecular surfactant, polycarboxylic acid molecules are adsorbed on the surface of powder materials through carboxyl groups to improve the dispersion ability of particles in the slurry state. Polyacrylamide is a water-soluble high molecular polymer that can increase the viscosity of foam and reduce foam fluidity, thus having a certain foam stabilizing effect. Sodium dodecylbenzenesulfonate is an anionic surfactant that has both foaming and foam stabilizing effects. Polyethylene glycol type alkyl acid polyoxyethylene ether makes the compounded material more stable and provides a certain air entraining effect, increasing the content of small bubbles in the material. In order to ensure that there are sufficient ions and pH values ​​in the material, potassium hydroxide and potassium chloride are added to increase the K ion content, and the slurry pH value is controlled by the potassium hydroxide content to ≥13; iron oxide powder is added to increase Fe 3+ content, improving electrical properties.

[0017] Foamed concrete is a widely used lightweight thermal insulation building material, and commonly used materials include cement, fly ash, mineral powder, lime and other materials. The composition of red mud is complex and the physical state is highly random, so there is less mature experience in foaming technology. The present invention combines the physical and chemical properties of red mud, and through experimental means, determines the foaming preparation technology with red mud as the main raw material, and explores the relationship between foaming ratio, material strength and components and preparation process. Original red mud mostly exists in the form of irregular agglomerates, and its dispersion degree can be improved by mechanical grinding and adding surfactants. In the batching process, the separate materials such as red mud, metakaolin, and aluminum powder are first stirred and dispersed at high speed, and then other components and remaining mixing water are added, and stirring is continued at a lower speed to prevent the bubbles that have been generated from being broken up, and then pouring and curing are carried out.

[0018] The beneficial effects of the present invention are as follows: the present invention forms a building-structure supercapacitor through the material component design of the interface functional layer and the energy storage and thermal insulation layer, which has both energy storage function. The interface functional layer acts as an electrode function, and the energy storage and thermal insulation layer acts as an electrolyte function, forming a multifunctional building material integrating thermal insulation and energy storage. The material can be combined with the building's bearing structure to realize the storage of new energy electricity such as light energy and wind energy generated by the building, and meet the daily electricity consumption of the building through the release of electricity, thereby contributing to the realization of "zero-carbon buildings". BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 Schematic diagram of the installation arrangement of the building material of the present invention.

[0020] Markings in the figure: 1. Cement-based wall / board; 2. Interface functional layer; 3. Energy storage and insulation layer; 4. Upper surface layer; 5. Decorative layer / photovoltaic panel; 6. Vertical partition board; 7. T-shaped metal embedded parts; 8. L-shaped metal embedded parts; 9. Energy storage control device. DETAILED DESCRIPTION

[0021] In order to better understand the present invention, the content of the present invention is further illustrated below in conjunction with the examples, but the content of the present invention is not limited to the following examples.

[0022] Example 1

[0023] As shown in the figure, a cement-based building material with integrated insulation and energy storage comprises an interface functional layer 2 and an energy storage insulation layer 3. The interface functional layer 2, attached to the inner surface of the cement-based wall / board 1, functions as a capacitor electrode material and provides energy storage. The energy storage insulation layer 3, located above the interface functional layer 2, offers excellent thermal insulation and energy storage capabilities. The interface functional layer 2 is 2.71mm thick, while the energy storage insulation layer 3, located above the interface functional layer 2, offers excellent thermal insulation and energy storage capabilities. The thickness of the energy storage insulation layer 3 is 80mm.

[0024] The cement-based wall / plate 1 is a load-bearing structural layer of a multifunctional building material with a load-bearing function; a vertical partition plate 6 is provided / installed on the surface of the cement-based wall / plate 1, and the vertical partition plate 6 divides the cement-based wall / plate 1 into squares, each square being an energy storage unit. T-shaped metal embedded parts 7 and L-shaped metal embedded parts 8 need to be embedded in the vertical partition plate 6, and energy transmission between the internal energy storage unit and the external control device is carried out through the T-shaped metal embedded parts 7 and the L-shaped metal embedded parts 8.

[0025] A method for preparing a cement-based thermal insulation and energy storage integrated building material comprises the construction of an interface functional layer and the pouring of an energy storage and thermal insulation layer.

[0026] The interface functional layer includes carbon fiber mesh and composite slurry. The carbon fiber mesh is cut according to the inner surface size of the frame composed of the wall / board and the vertical partition. The raw material components of the composite slurry are calculated by weight as follows: 40 parts of cementitious material; 35 parts of porous ceramsite; 60 parts of mixing water; 3 parts of graphene nanosheets; and 150 parts of dispersion liquid. The cementitious material is 42.5 grade ordinary Portland cement; the porous ceramsite is shale ceramsite with a particle size of ≤2 mm and a bulk density of 0.82 g / cm 3 The graphene nanosheet particles have a particle size of D502.77 μm and a specific surface area of ​​650 m 2 / g, thermal conductivity 4100w / m·K, electrical conductivity 185S / m; the dispersion is a polycarboxylic acid solution with a solid content of 38.5%; the carbon fiber mesh cloth should be 183μm thick and have a mesh size of 0.6mm.

[0027] The construction process of the interface functional layer includes the following steps: (1) preparation of graphene nanosheet dispersion: adding graphene nanosheets to 50 parts by weight of the dispersion, ultrasonically dispersing for 2 hours, and obtaining the graphene nanosheet dispersion; (2) conductive aggregate treatment: using porous ceramsite as a carrier, immersing the ceramsite in 4 parts by weight of the graphene nanosheet dispersion, and then transferring the dispersion to a stainless steel reactor, and performing hydrothermal treatment at 160°C for 12 hours; after the treatment, filtering the ceramsite, and drying it in a 60°C forced air drying oven for 2 hours to obtain a conductive aggregate; (3) composite slurry preparation: adding the conductive aggregate to the remaining parts by weight of the stone The graphene dispersion is moistened with half the weight of the mixing water and placed in a mixer. The mixture is stirred at a speed of 100 r / min and the cementitious material is slowly added during the stirring process. After the addition of the cementitious material, the mixture is stirred for 3 min. The remaining half of the mixing water is added and the mixture is stirred at a speed of 300 r / min on the mixer for 3 min to obtain a composite slurry. (4) Corrosion treatment and cutting of carbon fiber mesh cloth: The cut carbon fiber mesh is placed in a mixture of 1 mol / L concentrated HNO3 and 2 mol / L concentrated H2SO4 and heat treated at 60°C for 2 h. After treatment, it is repeatedly rinsed with deionized water until it is neutral. The mesh is cut according to the inner surface size of the frame composed of the wall / board and the vertical partition. (5) Construction of the interface functional layer: The prepared composite slurry is applied to the inner surface of the frame composed of the wall / board and the vertical partition board. The thickness of the coating is controlled to be 2~3 mm. Then, the carbon fiber mesh cloth cut according to the surface size of the cement-based wall / board is adhered after the corrosion treatment.

[0028] The interface functional layer acts as the electrode material of the capacitor. The measured key performance indicators of the interface functional layer 2 are: structural thickness 2.71mm, bonding strength 2.5MPa; area specific capacitance 735F / m 2 .

[0029] The raw materials for the energy storage and insulation layer are calculated by weight as follows: 70 parts red mud, 20 parts metakaolin, 5 parts sodium silicate, 3 parts aluminum powder, 3 parts foaming stabilizer; 1 part potassium hydroxide, 1 part potassium chloride, 2 parts iron oxide powder, and 55 parts mixing water. The red mud is undisturbed red mud discharged from the Bayer process electrolytic aluminum industry; the metakaolin is kaolin powder calcined at 750-850°C; the sodium silicate has a modulus of 1.2-1.5; the aluminum powder is a foaming aluminum powder with a mesh size of 100-150 and an active aluminum content of ≥98%. The foaming stabilizer is a mixture of polycarboxylic acid mother liquor, polyacrylamide, sodium dodecylbenzene sulfonate, and polyethylene glycol-type alkyl acid polyoxyethylene ether in a mass ratio of 1:0.4:0.2. The solids content of the foaming stabilizer after compounding is ≥40%.

[0030] The pouring process of the energy storage and thermal insulation layer comprises the following steps: (1) drying: drying the original red mud at a temperature of 80°C for a time of 0.5 to 1 hour, and controlling the moisture content of the material after drying to be less than 2%; (2) grinding: grinding and dispersing the dried red mud using a ball mill, and grinding for a time of 5 to 10 minutes, and controlling the particle size of the material after grinding to be 45 μm with a sieve residue of ≤3%; (3) mixing the ingredients: weighing red mud, metakaolin, and aluminum powder in proportion, adding 70% mixing water, mixing and stirring Mix on a mixer at a speed of 300 rpm / min for 5 minutes to form a slurry mixture; then mix sodium silicate, foaming stabilizer, potassium hydroxide, potassium chloride, iron oxide powder with 30% mixing water and add it to the slurry, and continue stirring at a speed of 150-200 rpm / min for 3 minutes to form a foaming slurry; (4) Pouring foaming: Pour the mixed slurry into the grid space of the cement-based wall / board where the interface functional layer has been constructed, and the mass of the poured slurry is 32 kg / m 2 , pouring thickness 80mm. After pouring, it needs to be covered with film and sealed for 3 days. After curing, the excess material is cut off along the upper surface with a cutting machine.

[0031] The measured value of the key performance indicators of the energy storage insulation layer 3 is: volume density 346kg / m 3 , thermal conductivity 0.0771W / m·K, ionic conductivity 0.046mS / cm; resistivity 34.3Ω·cm; it meets the requirements of light weight, heat preservation and energy storage, and acts as an internal filler and thermal insulation layer in terms of heat preservation function, and acts as an electrolyte component of supercapacitor in terms of energy storage function.

[0032] In this embodiment, the structure of the interface functional layer and the energy storage insulation layer are respectively produced and prepared using inorganic non-metallic composite materials of different components according to the above steps, forming a building material that integrates insulation and energy storage, and its storage energy density is 18.3W·h / m 2 .

[0033] Example 2

[0034] As shown in the figure, a cement-based integrated thermal insulation and energy storage building material includes an interface functional layer 2 and an energy storage insulation layer 3. The interface functional layer 2 is attached to the inner surface of the cement-based wall / board 1, has the function of a capacitor electrode material, and provides energy storage function. The thickness of the interface functional layer 2 is 2.46mm; the energy storage insulation layer 3 is located on the interface functional layer 2, has good thermal insulation capabilities, and also has energy storage function. The thickness of the energy storage insulation layer 3 is 90mm.

[0035] The cement-based wall / plate 1 is a load-bearing structural layer of a multifunctional building material with a load-bearing function; a vertical partition plate 6 should be provided / installed on the surface of the cement-based wall / plate 1, and the vertical partition plate 6 divides the cement-based wall / plate 1 into squares, each square being an energy storage unit, and T-shaped metal embedded parts 7 and L-shaped metal embedded parts 8 need to be embedded in the vertical partition plate 6, and energy transmission between the internal energy storage unit and the external control device is carried out through the T-shaped metal embedded parts 7 and the L-shaped metal embedded parts 8.

[0036] A method for preparing a cement-based thermal insulation and energy storage integrated building material comprises the construction of an interface functional layer and the pouring of an energy storage and thermal insulation layer.

[0037] The interface functional layer 2 includes a carbon fiber mesh and a composite slurry. The carbon fiber mesh is cut according to the surface area of ​​the cement-based wall / board. The raw material components of the composite slurry are calculated by weight as follows: 45 parts of cementitious material; 37 parts of porous ceramsite; 70 parts of mixing water; 3.6 parts of graphene nanosheets; and 180 parts of dispersion liquid. The cementitious material is 42.5 grade ordinary Portland cement; the porous ceramsite is shale ceramsite with a particle size of ≤2 mm and a bulk density of 0.82 g / cm 3 The graphene nanosheet particles have a particle size of D502.77 μm and a specific surface area of ​​650 m 2 / g, thermal conductivity 4100w / m·K, electrical conductivity 180S / m; the dispersion is a polycarboxylic acid solution with a solid content of ≥38.5%; the carbon fiber mesh cloth has a thickness of 190μm and a mesh size of 0.8mm.

[0038] The construction process of the interface functional layer 2 includes the following steps: (1) preparation of graphene nanosheet dispersion: adding graphene nanosheets to 50 parts by weight of the dispersion, ultrasonically dispersing for 2 hours, and obtaining the graphene nanosheet dispersion; (2) conductive aggregate treatment: using porous ceramsite as a carrier, immersing the ceramsite in 4 parts by weight of the graphene nanosheet dispersion, and then transferring the dispersion to a stainless steel reactor, and performing hydrothermal treatment at 160°C for 12 hours; after the treatment, the ceramsite is filtered and dried in a 60°C forced air drying oven for 2 hours to obtain a conductive aggregate; (3) composite slurry preparation: adding the conductive aggregate to the remaining parts by weight of the stone The graphene dispersion is moistened with half the weight of the mixing water and placed in a mixer. The mixture is stirred at a speed of 100 r / min and the cementitious material is slowly added during the stirring process. After the addition of the cementitious material, the mixture is stirred for 3 min. The remaining half of the mixing water is added and the mixture is stirred at a speed of 300 r / min on the mixer for 3 min to obtain a composite slurry. (4) Corrosion treatment and cutting of carbon fiber mesh cloth: The cut carbon fiber mesh is placed in a mixture of 1 mol / L concentrated HNO3 and 2 mol / L concentrated H2SO4 and heat treated at 60°C for 2 h. After treatment, it is repeatedly rinsed with deionized water until it is neutral. The mesh is cut according to the inner surface size of the frame composed of the wall / board and the vertical partition. (5) Construction of the interface functional layer: The prepared composite slurry is applied to the inner surface of the frame composed of the wall / board and the vertical partition board. The thickness of the coating is controlled to be 2~3 mm. Then, the carbon fiber mesh cloth cut according to the surface size of the cement-based wall / board is adhered after the corrosion treatment.

[0039] The interface functional layer 2 acts as the electrode material of the capacitor. The measured key performance indicators of the interface functional layer 2 are: structural thickness 2.46mm, bonding strength 1.9MPa; area specific capacitance 617F / m 2 .

[0040] The raw materials for the energy storage and thermal insulation layer 3 are calculated by weight as follows: 75 parts red mud, 20 parts metakaolin, 5 parts sodium silicate, 3.5 parts aluminum powder, 4 parts foaming stabilizer; 1.5 parts potassium hydroxide, 1.5 parts potassium chloride, 4 parts iron oxide powder, and 58 parts mixing water. The red mud is undisturbed red mud discharged from the Bayer process electrolytic aluminum industry; the metakaolin is kaolin powder calcined at 750-850°C; the sodium silicate has a modulus of 1.2-1.5; the aluminum powder is 100-150 mesh size foaming aluminum powder with an active aluminum content of ≥98%; the foaming stabilizer is a mixture of polycarboxylic acid mother liquor, polyacrylamide, sodium dodecylbenzene sulfonate, and polyethylene glycol-type alkyl acid polyoxyethylene ether in a mass ratio of 1:0.45:0.3. The solids content of the foaming stabilizer after compounding is ≥40%.

[0041] The pouring process of the energy storage and thermal insulation layer 3 includes the following steps: (1) drying: drying the original red mud at a temperature of 80°C for 0.5 to 1 hour, and controlling the moisture content of the material after drying to be less than 2%; (2) grinding: grinding and dispersing the dried red mud using a ball mill, and grinding for 5 to 10 minutes, and controlling the particle size of the material after grinding to be 45 μm with a sieve residue of ≤3%; (3) mixing the ingredients: weighing red mud, metakaolin, and aluminum powder in proportion, adding 70% mixing water, mixing and stirring them. , mix on a mixer at a speed of 300 rpm / min for 5 minutes to form a slurry mixture; then mix sodium silicate, foaming stabilizer, potassium hydroxide, potassium chloride, iron oxide powder with 30% mixing water and add to the slurry, and continue stirring at a speed of 150~200 rpm / min for 3 minutes to form a foaming slurry; (4) Pouring foaming: pour the mixed slurry into the grid space of the cement-based wall / board where the interface functional layer has been constructed, and the mass of the poured slurry is 31.3 kg / m 2 , pouring thickness 90mm. After pouring, it needs to be covered with film and sealed for 3 days. After curing, the excess material is cut off along the upper surface with a cutting machine.

[0042] The measured value of the key performance indicators of the energy storage insulation layer 3 is: volume density 318kg / m 3 , thermal conductivity 0.0715W / m·K, ionic conductivity 0.035mS / cm; resistivity 31.3Ω·cm; it meets the requirements of light weight, heat preservation and energy storage, and acts as an internal filler and thermal insulation layer in terms of heat preservation function, and acts as an electrolyte component of supercapacitor in terms of energy storage function.

[0043] In this embodiment, the structure of the interface functional layer and the energy storage insulation layer are respectively produced and prepared using inorganic non-metallic composite materials of different components according to the above steps, forming a building material that integrates insulation and energy storage, and its storage energy density is 18.9W·h / m 2 .

[0044] Example 3

[0045] As shown in the figure, a cement-based integrated thermal insulation and energy storage building material includes an interface functional layer 2 and an energy storage insulation layer 3. The interface functional layer 2 is attached to the inner surface of the cement-based wall / board 1, has the function of a capacitor electrode material, and provides energy storage function. The thickness of the interface functional layer 2 is 2.93mm; the energy storage insulation layer 3 is located on the interface functional layer 2, has good thermal insulation capabilities, and also has energy storage function. The thickness of the energy storage insulation layer 3 is 100mm.

[0046] The cement-based wall / plate 1 is a load-bearing structural layer of a multifunctional building material with a load-bearing function; a vertical partition plate 6 should be provided / installed on the surface of the cement-based wall / plate 1, and the vertical partition plate 6 divides the cement-based wall / plate 1 into squares, each square being an energy storage unit, and T-shaped metal embedded parts 7 and L-shaped metal embedded parts 8 need to be embedded in the vertical partition plate 6, and energy transmission between the internal energy storage unit and the external control device is carried out through the T-shaped metal embedded parts 7 and the L-shaped metal embedded parts 8.

[0047] A method for preparing a cement-based thermal insulation and energy storage integrated building material includes constructing an interface functional layer 2 and pouring an energy storage and thermal insulation layer 3.

[0048] The interface functional layer 2 includes a carbon fiber mesh and a composite slurry. The carbon fiber mesh is cut according to the surface area of ​​the cement-based wall / board. The raw material components of the composite slurry are calculated by weight as follows: 50 parts of cementitious material; 40 parts of porous ceramsite; 80 parts of mixing water; 4 parts of graphene nanosheets; and 200 parts of dispersion liquid. The cementitious material is 42.5 grade ordinary Portland cement; the porous ceramsite is shale ceramsite with a particle size of ≤2 mm and a bulk density of 0.82 g / cm 3 The graphene nanosheet particles have a particle size of D502.77 μm and a specific surface area of ​​650 m 2 / g, thermal conductivity 4100w / m·K, electrical conductivity 185S / m; the dispersion is a polycarboxylic acid solution with a solid content of 38.5%; the carbon fiber mesh cloth should be 185μm thick and have a mesh size of 0.3mm.

[0049] The construction process of the interface functional layer 2 includes the following steps: (1) preparation of graphene nanosheet dispersion: adding graphene nanosheets to 50 parts by weight of the dispersion, ultrasonically dispersing for 2 hours, and obtaining the graphene nanosheet dispersion; (2) conductive aggregate treatment: using porous ceramsite as a carrier, immersing the ceramsite in the graphene nanosheet dispersion, and then transferring the dispersion to a stainless steel reactor, and performing a hydrothermal treatment at 160°C for 12 hours; after the treatment, filtering the ceramsite, and drying it in a 60°C forced air drying oven for 2 hours to obtain a conductive aggregate; (3) composite slurry preparation: adding the remaining weight of the graphene to the conductive aggregate; The dispersion is moistened with half the weight of the mixing water, placed in a mixer, and stirred at a speed of 100 r / min. During the stirring process, the cementitious material is slowly added; after the addition of the cementitious material is completed, the stirring is continued for 3 minutes; the remaining half of the mixing water is added and stirred at a speed of 300 r / min on the mixer for 3 minutes to obtain a composite slurry; (4) Corrosion treatment and cutting of carbon fiber mesh cloth: the cut carbon fiber mesh is arranged in a mixture of 1 mol / L concentrated HNO3 and 2 mol / L concentrated H2SO4 and heat-treated at 60 ° C for 2 hours; after treatment, it is repeatedly rinsed with deionized water until neutral. Cut according to the inner surface size of the frame composed of the wall / board and the vertical partition; (5) Construction of the interface functional layer: the prepared composite slurry is applied to the inner surface of the frame composed of the wall / board and the vertical partition board, and the coating thickness is controlled to be 2~3 mm. Then, the carbon fiber mesh cloth cut according to the surface size of the cement-based wall / board is glued on after corrosion treatment.

[0050] The interface functional layer 2 acts as the electrode material of the capacitor. The measured key performance indicators of the interface functional layer 2 are: structural thickness 2.93mm, bonding strength 2.8MPa; area specific capacitance 852F / m 2 .

[0051] The raw materials for the energy storage and thermal insulation layer 3 are calculated by weight as follows: 75 parts red mud, 20 parts metakaolin, 5 parts sodium silicate, 4 parts aluminum powder, 5 parts foaming stabilizer; 2 parts potassium hydroxide, 2 parts potassium chloride, 5 parts iron oxide powder, and 60 parts mixing water. The red mud is undisturbed red mud discharged from the Bayer process electrolytic aluminum industry; the metakaolin is kaolin powder calcined at 750-850°C; the sodium silicate has a modulus of 1.2-1.5; the aluminum powder is a foaming aluminum powder with a mesh size of 100-150 and an active aluminum content of ≥98%. The foaming stabilizer is a mixture of polycarboxylic acid mother liquor, polyacrylamide, sodium dodecylbenzene sulfonate, and polyethylene glycol-type alkyl acid polyoxyethylene ether in a mass ratio of 1:0.4:0.3. The solids content of the foaming stabilizer after compounding is ≥40%.

[0052] The pouring process of the energy storage and thermal insulation layer 3 includes the following steps: (1) drying: drying the original red mud at a temperature of 80°C for 0.5 to 1 hour, and controlling the moisture content of the material after drying to be less than 2%; (2) grinding: grinding and dispersing the dried red mud using a ball mill, and grinding for 5 to 10 minutes, and controlling the particle size of the material after grinding to be 45 μm with a sieve residue of ≤3%; (3) mixing the ingredients: weighing red mud, metakaolin, and aluminum powder in proportion, adding 70% mixing water, mixing and stirring Mix on a mixer at a speed of 300 rpm / min for 5 minutes to form a slurry mixture; then mix sodium silicate, foaming stabilizer, potassium hydroxide, potassium chloride, iron oxide powder and 30% mixing water and add the slurry, and continue stirring at a speed of 150-200 rpm / min for 3 minutes to form a foaming slurry; (4) Pouring foaming: Pour the mixed slurry into the grid space of the cement-based wall / board where the interface functional layer has been constructed, and the mass of the poured slurry is 31 kg / m 2 , pouring thickness 100mm. After pouring, it needs to be covered with film and sealed for 3 days. After curing, use a cutting machine to cut off excess material along the upper surface.

[0053] The measured value of the key performance indicators of the energy storage insulation layer 3 is: volume density 309kg / m 3 , thermal conductivity is 0.0719W / m·K, ionic conductivity is 0.062mS / cm; resistivity is 36.5Ω·cm; it meets the requirements of light weight, heat preservation and energy storage, and acts as an internal filler and thermal insulation layer in terms of heat preservation function, and acts as an electrolyte component of supercapacitor in terms of energy storage function.

[0054] In this embodiment, the structures of the interface functional layer 2 and the energy storage insulation layer 3 are respectively produced and prepared using inorganic non-metallic composite materials of different components according to the above steps, forming a building material that integrates insulation and energy storage, and its storage energy density is 21.2W·h / m 2 .

[0055] An upper boundary layer 4 can be cast on the energy storage and insulation layer 3 of the building material of the present invention, which serves as an encapsulation and protective layer for the building material. The outer surface of the upper boundary layer 4 is provided with a surface functional layer, an energy storage control device 9 and other external structural layers according to the use requirements of the building. A typical scenario for the surface functional layer is the decorative layer / photovoltaic panel 5 on the outer surface of the building, etc. The energy storage control device 9 is a control and regulation unit for the power storage of the building material, and the corresponding circuit design and installation need to be carried out according to the overall design of the building and the application scenario. According to the actual situation of the project, the pre-buried T-shaped metal embedded parts 7 and L-shaped metal embedded parts 8 can be used for combined installation in the factory, or they can be installed on the construction site. The present invention only relates to the design of the components, preparation process and performance of the building materials, and does not involve the application design of external structural layers such as the surface functional layer for specific building forms.

[0056] The above embodiments are merely examples of the explanation, specific embodiments, and implementation effects of the present invention, and are not intended to limit the present invention. Based on the present disclosure, some modifications or improvements without creative contributions may be made thereto, which will be apparent to those skilled in the art. Therefore, these modifications or improvements made without departing from the spirit of the present disclosure are intended to fall within the scope of protection claimed in the present disclosure.

Claims

1. A cement-based thermal insulation and energy storage integrated building material, characterized by: It includes an interface functional layer and an energy storage insulation layer. The interface functional layer is attached to the surface of the cement-based wall / board, has the function of a capacitor electrode material, and provides energy storage function. The thickness of the interface functional layer is 2~3mm. The key performance indicators of the interface functional layer are: bonding strength ≥1Mpa, area specific capacitance ≥500F / m 2 The energy storage insulation layer is located above the interface functional layer and serves as the insulation layer of the building wall. It has good thermal insulation capabilities and energy storage functions. The thickness of the energy storage insulation layer is 80~100mm. The key performance indicators of the energy storage insulation layer are: volume density 300~350kg / m 3 , thermal conductivity 0.07~0.08W / m·K, ionic conductivity ≥0.03mS / cm, resistivity ≤50Ω·cm; The interface functional layer includes carbon fiber mesh and composite slurry. The carbon fiber mesh is cut according to the surface area of ​​the cement-based wall / board. The raw material components of the composite slurry are calculated by weight as follows: 40-50 parts of cementitious material; 35-40 parts of porous ceramsite; 3-4 parts of graphene nanosheets; 150-200 parts of dispersion liquid; and 60-80 parts of mixing water. The raw material components of the energy storage and insulation layer are calculated by weight: 70-75 parts of red mud, 20 parts of metakaolin, 5 parts of sodium silicate, 3-4 parts of aluminum powder, 3-5 parts of foaming stabilizer; 1-2 parts of potassium hydroxide, 1-2 parts of potassium chloride, 2-5 parts of iron oxide powder, and 55-60 parts of mixing water.

2. The cement-based thermal insulation and energy storage integrated building material according to claim 1, characterized in that: The interface functional layer and the energy storage insulation layer are constructed based on the building cement-based wall / building board. The cement-based wall / board is the load-bearing structural layer of the multifunctional building material and has the load-bearing function. The surface of the cement-based wall / board is provided with a vertical partition plate. The vertical partition plate divides the surface of the cement-based wall / board into squares. The space inside the square is used to fill the interface functional layer and the energy storage insulation layer material. Each square is an energy storage unit. The vertical partition plate is made of cement-based material or other inorganic material. T-shaped metal embedded parts and L-shaped metal embedded parts are embedded in the vertical partition plate. The vertical partition plate is anchored by the T-shaped metal embedded parts and the L-shaped metal embedded parts, and the energy transmission between the internal energy storage unit and the external control device is carried out.

3. The cement-based thermal insulation and energy storage integrated building material according to claim 1, characterized in that: The cementitious material is 42.5 grade ordinary Portland cement; the porous ceramsite is shale ceramsite with a particle size of ≤2mm and a bulk density of ≤0.85g / cm 3 .

4. The cement-based thermal insulation and energy storage integrated building material according to claim 1, characterized in that: The particle size of graphene nanosheets should be ≤3μm, the thickness should be 5~50nm, and the specific surface area should be ≥600m 2 / g, thermal conductivity ≥3500w / m·K, electrical conductivity ≥100S / m.

5. The cement-based thermal insulation and energy storage integrated building material according to claim 1, characterized in that: The dispersion is a polycarboxylic acid solution with a solid content of ≥35%.

6. The cement-based thermal insulation and energy storage integrated building material according to claim 1, characterized in that: The thickness of carbon fiber mesh cloth is ≤200μm, and the mesh size is 0.3~0.8mm.

7. The cement-based thermal insulation and energy storage integrated building material according to claim 1, characterized in that: Red mud is the original red mud discharged from the Bayer process electrolytic aluminum industry; metakaolin is the powder obtained by calcining kaolin powder at 750~850℃.

8. The cement-based thermal insulation and energy storage integrated building material according to claim 1, characterized in that: The modulus of sodium silicate is 1.2~1.5; the aluminum powder is foaming aluminum powder with a mesh size of 100~150, and the active aluminum content is ≥98%.

9. The cement-based thermal insulation and energy storage integrated building material according to claim 1, characterized in that: The foaming stabilizer is compounded by polycarboxylic acid mother liquor, polyacrylamide, sodium dodecylbenzene sulfonate and polyethylene glycol type alkyl acid polyoxyethylene ether, and the mass ratio of the three is 1: (0.4~0.45): (0.2~0.3). The solid content of the compounded foaming stabilizer is ≥40%.

10. A method for preparing the cement-based thermal insulation and energy storage integrated building material according to claim 1, characterized in that: Including the construction of the interface functional layer and the pouring of the energy storage and thermal insulation layer; The raw material processing and construction process of the interface functional layer includes the following steps: (1) preparation of graphene nanosheet dispersion: adding graphene nanosheets to 50 parts by weight of the dispersion, ultrasonically dispersing for 2 hours, and obtaining the graphene nanosheet dispersion; (2) conductive aggregate treatment: using porous ceramsite as a carrier, immersing the ceramsite in 4 parts by weight of the graphene nanosheet dispersion, and then transferring the dispersion to a stainless steel reactor and performing a hydrothermal treatment at 160°C for 12 hours; after the treatment, the ceramsite is filtered and dried in a 60°C forced air drying oven for 2 hours to obtain a conductive aggregate; (3) composite slurry preparation: adding the conductive aggregate to the remaining parts by weight of the graphene dispersion, wetting it with half the weight of the mixing water, putting it into a mixer, stirring at a speed of 100 r / min, and slowly adding the gelling material during the stirring process; After the addition of the cementitious material is completed, continue stirring for 3 minutes; add the remaining half of the mixing water and stir at a speed of 300r / min on the mixer for 3 minutes to obtain a composite slurry; (4) Corrosion treatment and cutting of carbon fiber mesh cloth: arrange the cut carbon fiber mesh in a mixture of 1mol / L concentrated HNO3 and 2mol / L concentrated H2SO4, and heat treat it at 60℃ for 2h; after treatment, rinse it repeatedly with deionized water until it is neutral; cut it according to the inner surface size of the frame composed of the wall / board and the vertical partition board; (5) Construction of the interface functional layer: apply the prepared composite slurry on the inner surface of the frame composed of the wall / board and the vertical partition board, and control the coating thickness to be 2~3mm, and then stick the carbon fiber mesh cloth cut according to the surface size of the cement-based wall / board after corrosion treatment; The raw material processing and pouring process of the energy storage insulation layer includes the following steps: (1) drying: drying the original red mud at a temperature of 80°C for 0.5 to 1 hour, and controlling the moisture content of the material after drying to be less than 2%; (2) grinding: grinding and dispersing the dried red mud using a ball mill, and grinding for 5 to 10 minutes, and controlling the particle size of the material after grinding to be 45 μm with a sieve residue of ≤3%; (3) mixing the ingredients: weighing red mud, metakaolin, and aluminum powder in proportion, adding 70% mixing water, mixing them, and Stirring, mixing on a mixer at a speed of 300 rpm / min for 5 minutes to form a slurry mixture; then, sodium silicate, foaming stabilizer, potassium hydroxide, potassium chloride, iron oxide powder and 30% mixing water are mixed and added to the slurry, and stirring is continued at a speed of 150-200 rpm / min for 3 minutes to form a foaming slurry; (4) Pouring foaming: Pour the stirred slurry into the grid space of the cement-based wall / board where the interface functional layer has been constructed, and the mass of the poured slurry is 30-35 kg / m 2 .

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