A cement-based integrated thermal insulation and energy storage building material and its preparation method

Abstract

This invention belongs to the field of building materials technology and discloses a cement-based integrated thermal insulation and energy storage building material and its preparation method. It includes an interface functional layer and an energy storage insulation layer. The interface functional layer is attached to the surface of a cement-based wall / board and functions as an electrode material for a capacitor. The thickness of the interface functional layer is 2-3 mm. The energy storage insulation layer is located above the interface functional layer and has good thermal insulation capabilities, while also serving as an energy storage function. The thickness of the energy storage insulation layer is 80-100 mm. Through the material composition design of the interface functional layer and the energy storage insulation layer, this invention constitutes a building-structure supercapacitor with energy storage capabilities. The interface functional layer acts as an electrode, and the energy storage insulation layer acts as an electrolyte, forming an integrated thermal insulation and energy storage building material. This material can be combined with the building's load-bearing structure to store new energy sources such as solar and wind power generated by the building and release the electricity to meet the building's daily electricity needs.

Description

Technical Field

[0001] This invention belongs to the field of building materials technology, specifically relating to a cement-based integrated thermal insulation and energy storage building material and its preparation method. Background Technology

[0002] Photovoltaic power generation technology has been widely applied to building walls and roofs. Given the enormous surface area and volume of building structures, utilizing this vast surface area for power generation not only allows for the production of more electricity through external photovoltaics but also enables 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 buildings. Currently, electricity storage primarily employs chemical battery energy storage, but these batteries are costly, require specially designed installation spaces, and pose certain risks of leakage and pollution. How to store and regulate electricity after it is generated remains a major technical challenge for building-integrated photovoltaic (BIPV) power generation.

[0003] The design of building exterior wall insulation layers is currently an important measure to reduce energy consumption and improve housing comfort. Insulation layers often utilize lightweight, porous inorganic materials such as rock wool, rock slabs, and foamed boards. Through their porous structure and the low thermal conductivity of inorganic materials, they achieve the thermal insulation function of building exterior walls. However, without increasing additional space occupation, how to utilize the internal volume and composition of building materials for energy storage, achieving the storage and regulation of new energy power, and thus enabling building walls to have integrated functions such as thermal insulation and energy storage, is a problem that urgently needs to be solved. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a cement-based integrated thermal insulation and energy storage building material and its preparation method. Targeting the development needs of smart cities for multifunctional and green buildings, the invention specifically designs the thermal insulation layer material for building exterior walls and adds an interface functional layer between the cement-based wall and the thermal insulation layer material, thereby endowing the building wall with integrated energy storage and thermal insulation functions.

[0005] To achieve the above objectives, the technical solution adopted by this invention is as follows: a cement-based integrated thermal insulation and energy storage building material, comprising an interface functional layer and an energy storage and thermal insulation layer. The interface functional layer is attached to the surface of a cement-based wall / board and functions as an electrode material for a capacitor. 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 capacitance ≥ 500 F / m². 2 The energy storage insulation layer is located above the interface functional layer, possessing excellent thermal insulation capabilities and also serving as an electrolyte layer. The thickness of the energy storage insulation layer is 80-100mm, and its key performance indicators are: bulk density 300-350kg / m³. 3Thermal conductivity 0.07~0.08 W / m·K, ionic conductivity ≥0.03 mS / cm; resistivity ≤50 Ω·cm.

[0006] The interface functional layer and energy storage insulation layer are constructed based on the building's cement-based walls / building panels. The cement-based walls / panels serve as the load-bearing structural layer of the multi-functional building material, possessing load-bearing capabilities. Vertical partitions are installed on the surface of the cement-based walls / panels, dividing the surface into squares. The spaces within these squares are used to fill the interface functional layer and energy storage insulation layer materials. Each square is an energy storage unit, the size of which can be designed according to the building form and energy storage application scenario. The vertical partitions can be made of cement-based materials or other inorganic materials. T-shaped and L-shaped metal embedded parts are pre-embedded in the vertical partitions for anchoring the vertical partitions and for energy transmission between the internal energy storage units and external control devices.

[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 by weight: 40-50 parts of cementitious material; 35-40 parts of porous ceramsite; 3-4 parts of graphene nanosheets; and 150-200 parts of dispersion.

[0008] The cementing material is 42.5 grade ordinary Portland cement;

[0009] The porous ceramsite is made from shale ceramsite with a particle size ≤2mm and a bulk density ≤0.85g / cm³. 3 ;

[0010] The graphene nanosheets should have a particle size D50 ≤ 3 μm, a thickness of 5~50 nm, and a specific surface area ≥ 600 m². 2 / g, thermal conductivity ≥3500w / m·K, electrical conductivity ≥100S / m;

[0011] The dispersion is a polycarboxylic acid solution with a solid content of ≥35%;

[0012] The thickness of the carbon fiber mesh should be ≤200μm, and the mesh size should be 0.3~0.8mm.

[0013] The raw material components of the energy storage and insulation layer are as follows by weight: 70-75 parts red mud, 20 parts metakaolin, 5 parts sodium silicate, 3-4 parts aluminum powder, 3-5 parts foaming stabilizer; 1-2 parts potassium hydroxide, 1-2 parts potassium chloride, 2-5 parts iron oxide powder, and 55-60 parts mixing water.

[0014] The red mud is the original red mud discharged from the Bayer process of aluminum electrolysis; the metakaolin is the powder obtained by calcining kaolin powder at 750~850℃.

[0015] The sodium silicate has a modulus of 1.2 to 1.5; the aluminum powder is a foaming aluminum powder with a mesh size of 100 to 150 and an active aluminum content of ≥98%.

[0016] The foaming stabilizer is composed of polycarboxylic acid mother liquor, polyacrylamide, sodium dodecylbenzene sulfonate, and polyethylene glycol-type alkyl acid polyoxyethylene ether, with a mass ratio of 1:(0.4~0.45):(0.2~0.3). The solid content of the foaming stabilizer after compounding is ≥40%.

[0017] A method for preparing a cement-based integrated thermal insulation and energy storage building material includes the construction of an interface functional layer and the pouring of an energy storage and thermal insulation layer.

[0018] The raw material processing and construction process of the interface functional layer includes the following steps: (1) Preparation of graphene nanosheet dispersion: Add graphene nanosheets to 50 parts by weight of dispersion and ultrasonically disperse for 2 hours to obtain graphene nanosheet dispersion; (2) Conductive aggregate treatment: Using porous ceramic particles as carrier, soak the ceramic particles in 4 parts by weight of graphene nanosheet dispersion, and then transfer the dispersion to a stainless steel reactor and perform hydrothermal treatment at 160°C for 12 hours; after treatment, filter the ceramic particles and dry them in a 60°C forced-air drying oven for 2 hours to obtain conductive aggregate; (3) Preparation of composite slurry: Add the conductive aggregate to the remaining weight Half of the graphene dispersion was wetted with half of the mixing water and placed in a mixer. The mixer was started at a speed of 100 r / min. During the mixing process, the cementitious material was slowly added. After the cementitious material was added, the mixer was continued for 3 min. The remaining half of the mixing water was added and the mixer was stirred at a speed of 300 r / min for 3 min to obtain the composite slurry. (4) Corrosion treatment and cutting of carbon fiber mesh: The cut carbon fiber mesh was placed in a mixture of 1 mol / L concentrated HNO3 and 2 mol / L concentrated H2SO4 and heat-treated at 60℃ for 2 h. After treatment, it was repeatedly rinsed with deionized water until neutral. Cut according to the inner surface dimensions of the frame composed of the wall / board and the vertical partition plate. (5) Construction of the interface functional layer: The prepared composite slurry was brushed on the inner surface of the frame composed of the wall / board and the vertical partition plate. The coating thickness was controlled at 2~3 mm. Then the cut carbon fiber mesh was attached.

[0019] The raw material processing and casting process of the energy storage insulation layer includes the following steps: (1) Drying: Dry the original red mud at 80℃ for 0.5-1h, and control the moisture content of the material after drying to be <2%; (2) Grinding: Grind and disperse the dried red mud using a ball mill for 5-10min, and control the particle size of the material after grinding to be ≤3% on a 45μm sieve; (3) Mixing: Weigh red mud, metakaolin, and aluminum powder according to the proportion, add 70% mixing water, mix them and carry out the mixing process. Stirring: Mix at 300 rpm / min for 5 minutes on a mixer to form a slurry mixture; then add sodium silicate, foaming stabilizer, potassium hydroxide, potassium chloride, iron oxide powder and 30% mixing water to the slurry, and continue stirring at 150~200 rpm / min for 3 minutes to form a foamed slurry; (4) Pouring foam: Pour the mixed slurry into the grid space of the cement-based wall / board that has been constructed with the interface functional layer, with a pouring slurry mass of 30~35 kg / m 2 .

[0020] The basic principle of this invention:

[0021] This invention relates to a cement-based building material integrating energy storage and thermal insulation. Energy transfer between the external environment and the internal energy storage unit is achieved through T-shaped and L-shaped metal embedded parts pre-embedded in vertical partitions arranged on the outer surface of the cement-based wall / board. Simultaneously, the T-shaped and L-shaped metal embedded parts act as anchors in the structure, improving the overall reliability of the cement-based wall / board. The interface functional layer is a functional component attached between the cement-based wall / board and the insulation material, possessing high specific surface area, high electrical conductivity, good mechanical properties, and electrochemical stability, meeting the energy storage requirements of the building material. The energy storage insulation layer is a filler component above the interface functional layer. It is lightweight and porous, reducing the overall weight of building materials while having a low heat transfer coefficient, thus providing good thermal insulation capabilities. It serves as both a filler and a thermal insulation layer in terms of thermal insulation. At the same time, the porous structure can store ions and provide channels for ion transport, thus acting as an electrolyte component of a supercapacitor in terms of energy storage, meeting the energy storage requirements of building materials. The thermal insulation function is mainly achieved through the low thermal conductivity of the energy storage insulation layer, while the energy storage function is realized through the supercapacitor formed by the combination of the interface functional layer and the energy storage insulation layer to store electrical energy.

[0022] Supercapacitor electrodes store charge through electrostatic adsorption. Carbon materials such as graphite, carbon fiber, carbon nanotubes, and graphene possess long-term cycling stability and are commonly used in electrode material preparation. This invention utilizes multilayer graphene oxide nanosheets as the electrode active material. Graphene is a high-performance nanomaterial with small particles and a large specific surface area, thus exhibiting small size effects, surface effects, quantum effects, and interface effects. Graphene's electron mobility exceeds 15000 cm⁻¹.2 / (V•S), while the resistivity is only about 10 -6 With a low resistivity (Ω•cm), 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 5 nm to 50 nm, whose properties are closer to those of monolayer graphene oxide. To overcome the aggregation of graphene nanosheets and improve their electrical properties, this invention employs a polycarboxylic acid solution for dispersion. Through the adsorption of carboxylic acid molecules and steric hindrance, the hydrophobic graphene nanosheets acquire a certain degree of hydrophilicity, improving the compatibility and dispersion ability of graphene nanosheets with cement-based materials, making them suitable as electrode active materials in cement-based composite materials.

[0023] To improve the effective density of electrode materials in the functional layer of the interface, this 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, and agriculture. Its low density and porous structure provide excellent adsorption properties, and it is also commonly used as aggregate in lightweight insulating concrete. This invention uses a vacuum hydrothermal method to prepare conductive aggregates, and then carries graphene nanosheets within the porous interior of the aggregates. This increases the graphene nanosheet content at the electrode transition interface, thereby improving the electrical properties of the electrode material.

[0024] This invention utilizes etched carbon fiber mesh as a current collector for loading active materials. Carbon fiber is an excellent electrode current collector material, possessing superior mechanical properties, chemical / electrochemical stability, and good conductivity. However, due to its low specific surface area and surface activity, the electrochemical storage capacity of carbon fiber electrodes is very small. Therefore, the carbon fiber mesh needs to be pre-etched; this etching process improves the surface defects and the load-bearing capacity of the conductive medium on the carbon fiber mesh.

[0025] Red mud is a byproduct of the alumina industrial production process. my country's electrolytic aluminum industry is massive, with annual emissions exceeding 100 million tons. Large stockpiles of red mud not only occupy land but also severely impact the environment and the industry's sustainable development. Red mud is a highly alkaline solid waste, primarily composed of Si, Al, Fe, Ca, Na, and K, with a pH range generally between 10 and 13. The content of Al₂O₃ + Fe₂O₃ typically exceeds 50%, and its main minerals include hematite, nepheline, calcite, boehmite, and gibbsite. The microstructure of red mud is relatively loose, mainly composed of irregularly shaped red mud particles. These undisturbed red mud aggregates possess abundant pores with diameters approximately 0.2–0.5 μm. The particles exhibit a large specific surface area, high water absorption, and strong water retention, providing storage and transport channels for Fe and Al ions, making it an ideal solid electrolyte matrix material. Combining chemical foaming technology can further improve its porosity and pore structure, achieving a stable porous physical structure for the internal material. Metakaolin, a product of kaolin activated at high temperature, is a highly active aluminosilicate raw material. Under alkaline conditions, it can polymerize to form aluminosilicate cementitious materials with an amorphous to semi-crystalline three-dimensional structure. This invention utilizes sodium silicate as an activation agent and metakaolin as a polymerizing agent to achieve a certain mechanical strength for the internal filling material. Aluminum powder is used as a foaming agent to achieve foaming of the internal filling material. Aluminum powder releases hydrogen gas when reacting with water and alkaline substances, which can form pores inside the material, making it 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, improving the conductivity of the internal filling material. A self-made foaming stabilizer is used to improve the stability of the structure after foaming. The foaming stabilizer is compounded from polycarboxylic acid mother liquor, polyacrylamide, sodium dodecylbenzene sulfonate, and polyethylene glycol-type alkyl acid polyoxyethylene ether. Polycarboxylic acid molecules, as macromolecular surfactants, improve particle dispersion in slurry states by adsorbing onto the surface of powder materials through carboxyl groups. Polyacrylamide, a water-soluble polymer, can increase foam viscosity and reduce foam flowability, thus exhibiting a certain foam stabilizing effect. Sodium dodecylbenzenesulfonate, an anionic surfactant, has both foaming and foam-stabilizing effects. Polyethylene glycol-type alkyl acid polyoxyethylene ethers further stabilize the compounded material and provide a certain air-entraining effect, increasing the content of small bubbles in the material. To ensure sufficient ions and pH value in the material, potassium hydroxide and potassium chloride are added to increase the K ion content, and the pH value of the slurry is controlled to be ≥13 by the potassium hydroxide content; iron oxide powder is added to increase the Fe ion content. 3+ Increase content to improve electrical performance.

[0026] Foamed concrete is a widely used lightweight thermal insulation building material, commonly made from materials such as cement, fly ash, mineral powder, and lime. Red mud has a complex composition and highly random physical state, resulting in limited mature experience in foaming technology. This invention, combining the physicochemical properties of red mud, experimentally determined a foaming preparation technology using red mud as the main raw material, elucidating the relationship between foaming ratio, material strength, composition, and preparation process. Raw red mud often exists as irregular aggregates, which can be dispersed by mechanical grinding and the addition of surface-active components. In the batching process, red mud, metakaolin, aluminum powder, and other separate materials are first dispersed by high-speed stirring. Then, other components and remaining mixing water are added, and stirring continues at a lower speed to prevent the already generated air bubbles from being broken up. Finally, pouring and curing are carried out.

[0027] The beneficial effects of this invention are as follows: This invention, through the material composition design of the interface functional layer and the energy storage and insulation layer, constitutes a building-structure supercapacitor that also has an energy storage function. The interface functional layer acts as an electrode, and the energy storage and insulation layer acts as an electrolyte, forming a multifunctional building material that integrates insulation and energy storage. It can be combined with the building's load-bearing structure to store new energy power such as solar and wind power generated by the building, and meet the building's daily electricity needs through the release of electricity, thus contributing to the realization of "zero-carbon buildings". Attached Figure Description

[0028] Figure 1 This is a schematic diagram of the installation layout of the building materials of the present invention.

[0029] The markings in the diagram are: 1. Cement-based wall / board; 2. Interface functional layer; 3. Energy storage and insulation layer; 4. Top surface layer; 5. Decorative layer / photovoltaic panel; 6. Vertical partition plate; 7. T-shaped metal embedded part; 8. L-shaped metal embedded part; 9. Energy storage control device. Detailed Implementation

[0030] To better understand the present invention, the following embodiments further illustrate the content of the present invention, but the content of the present invention is not limited to the following embodiments.

[0031] Example 1

[0032] 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 and functions as an electrode material for a capacitor, providing energy storage functionality. The energy storage insulation layer 3 is located above the interface functional layer 2, possessing good thermal insulation capabilities and also serving as an energy storage function. The thickness of the interface functional layer 2 is 2.71 mm; the thickness of the energy storage insulation layer 3 is 80 mm.

[0033] The cement-based wall / board 1 is a load-bearing structural layer of multifunctional building materials, with load-bearing function; vertical partition plates 6 are set / installed on the surface of the cement-based wall / board 1, which divide the cement-based wall / board 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 pre-embedded in the vertical partition plates 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 L-shaped metal embedded parts 8.

[0034] A method for preparing a cement-based integrated thermal insulation and energy storage building material includes the construction of an interface functional layer and the pouring of an energy storage and thermal insulation layer.

[0035] The interface functional layer includes carbon fiber mesh and composite slurry. The carbon fiber mesh is cut according to the inner surface dimensions of the frame formed by the wall / board and the vertical partition. The raw material components of the composite slurry, by weight, are: 40 parts cementitious material; 35 parts porous ceramsite; 60 parts mixing water; 3 parts graphene nanosheets; and 150 parts dispersion. The cementitious material is 42.5 grade ordinary Portland cement. The porous ceramsite is shale ceramsite with a particle size ≤2mm and a bulk density of 0.82g / cm³. 3 The graphene nanosheets have a particle size D50 of 2.77 μm and a specific surface area of ​​650 m². 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 should have a thickness of 183μm and a mesh size of 0.6mm.

[0036] The construction process of the interface functional layer includes the following steps: (1) Preparation of graphene nanosheet dispersion: Add graphene nanosheets to 50 parts by weight of dispersion and ultrasonically disperse for 2 hours to obtain graphene nanosheet dispersion; (2) Conductive aggregate treatment: Using porous ceramic particles as a carrier, soak the ceramic particles in 4 parts by weight of graphene nanosheet dispersion, and then transfer the dispersion to a stainless steel reactor and perform hydrothermal treatment at 160°C for 12 hours; after treatment, filter the ceramic particles and dry them in a 60°C forced-air drying oven for 2 hours to obtain conductive aggregate; (3) Preparation of composite slurry: Add the conductive aggregate to the remaining parts by weight of graphene nanosheet dispersion. The graphene dispersion was moistened with half the weight of mixing water and placed in a mixer. The mixer was started at a speed of 100 r / min. During the mixing process, the cementitious material was slowly added. After the cementitious material was added, the mixer was continued for 3 min. The remaining half of the mixing water was added and the mixer was stirred at a speed of 300 r / min for 3 min to obtain the composite slurry. (4) Corrosion treatment and cutting of carbon fiber mesh: The cut carbon fiber mesh was placed in a mixture of 1 mol / L concentrated HNO3 and 2 mol / L concentrated H2SO4 and heat-treated at 60℃ for 2 h. After treatment, it was 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 plate. (5) Construction of the interface functional layer: The prepared composite slurry was brushed on the inner surface of the frame composed of the wall / board and the vertical partition plate. The coating thickness was controlled at 2~3 mm. Then, the carbon fiber mesh cut according to the surface size of the cement-based wall / board was glued on after corrosion treatment.

[0037] The interface functional layer functions as the electrode material of the capacitor. The measured key performance indicators of interface functional layer 2 are: structural thickness of 2.71 mm, adhesive strength of 2.5 MPa, and areal capacitance of 735 F / m². 2 .

[0038] The raw material components of the energy storage and insulation layer, by weight, are: 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 virgin red mud discharged from the Bayer process of aluminum electrolysis; the metakaolin is kaolin powder obtained by calcining at 750-850℃; the sodium silicate has a modulus of 1.2-1.5; the aluminum powder is foaming aluminum powder with a mesh size of 100-150 and an active aluminum content ≥98%; the foaming stabilizer is a compound of polycarboxylic acid mother liquor, polyacrylamide, sodium dodecylbenzene sulfonate, and polyethylene glycol-type alkyl acid polyoxyethylene ether, with a mass ratio of 1:0.4:0.2, and the solid content of the compounded foaming stabilizer is ≥40%.

[0039] The casting process of the energy storage insulation layer includes the following steps: (1) Drying: Dry the original red mud at 80℃ for 0.5-1h, and control the moisture content of the material after drying to be <2%; (2) Grinding: Grind and disperse the dried red mud using a ball mill for 5-10min, and control the particle size of the material after grinding to be ≤3% on a 45μm sieve; (3) Batching and mixing: Weigh red mud, metakaolin, and aluminum powder according to the proportion, add 70% mixing water, mix them and stir. Mix at 300 rpm / min for 5 minutes to form a slurry mixture; then add sodium silicate, foaming stabilizer, potassium hydroxide, potassium chloride, iron oxide powder and 30% mixing water to the slurry, and continue mixing at 150~200 rpm / min for 3 minutes to form a foamed slurry; (4) pouring foam: pour the mixed slurry into the grid space of the cement-based wall / board that has been constructed with the interface functional layer, with a pouring slurry mass of 32 kg / m 2 The pouring thickness is 80mm. After pouring, it needs to be covered and sealed for 3 days for curing. After curing, use a cutting machine to remove excess material along the top surface.

[0040] The measured key performance indicators of the energy storage insulation layer 3 are: bulk density 346 kg / m³ 3 It has a thermal conductivity of 0.0771 W / m·K, an ionic conductivity of 0.046 mS / cm, and a resistivity of 34.3 Ω·cm. It meets the requirements of being lightweight, heat-insulating, and energy-storing. In terms of heat insulation, it serves as an internal filler and heat insulation layer, and in terms of energy storage, it serves as an electrolyte component of a supercapacitor.

[0041] In this embodiment, the interface functional layer and the energy storage and insulation layer are manufactured using inorganic non-metallic composite materials of different components according to the above steps, forming an integrated building material for heat insulation and energy storage, with a storage energy density of 18.3 W·h / m³. 2 .

[0042] Example 2

[0043] 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, and has the function of an electrode material for a capacitor, providing 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 capacity, and also has energy storage function. The thickness of the energy storage insulation layer 3 is 90mm.

[0044] The cement-based wall / board 1 is a load-bearing structural layer of multifunctional building materials, with load-bearing function; vertical partition plates 6 should be set / installed on the surface of the cement-based wall / board 1, the vertical partition plates 6 divide the cement-based wall / board 1 into squares, each square is an energy storage unit, T-shaped metal embedded parts 7 and L-shaped metal embedded parts 8 need to be pre-embedded in the vertical partition plates 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 L-shaped metal embedded parts 8.

[0045] A method for preparing a cement-based integrated thermal insulation and energy storage building material includes the construction of an interface functional layer and the pouring of an energy storage and thermal insulation layer.

[0046] The interface functional layer 2 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, by weight, are: 45 parts cementitious material; 37 parts porous ceramsite; 70 parts mixing water; 3.6 parts graphene nanosheets; and 180 parts dispersion. The cementitious material is 42.5 grade ordinary Portland cement. The porous ceramsite is shale ceramsite with a particle size ≤2mm and a bulk density of 0.82g / cm³. 3 The graphene nanosheets have a particle size D50 of 2.77 μm and a specific surface area of ​​650 m². 2 / g, thermal conductivity 4100w / m·K, electrical conductivity 180S / m; the dispersion is a polycarboxylic acid solution with a solid content ≥38.5%; the carbon fiber mesh is 190μm thick and has a mesh size of 0.8mm.

[0047] The construction process of the interface functional layer 2 includes the following steps: (1) Preparation of graphene nanosheet dispersion: Add graphene nanosheets to 50 parts by weight of dispersion and ultrasonically disperse for 2 hours to obtain graphene nanosheet dispersion; (2) Conductive aggregate treatment: Using porous ceramic particles as a carrier, soak the ceramic particles in 4 parts by weight of graphene nanosheet dispersion, and then transfer the dispersion to a stainless steel reactor and perform hydrothermal treatment at 160°C for 12 hours; after treatment, filter the ceramic particles and dry them in a 60°C forced-air drying oven for 2 hours to obtain conductive aggregate; (3) Preparation of composite slurry: Add the conductive aggregate to the remaining parts by weight of graphene nanosheet dispersion. The graphene dispersion was moistened with half the weight of mixing water and placed in a mixer. The mixer was started at a speed of 100 r / min. During the mixing process, the cementitious material was slowly added. After the cementitious material was added, the mixer was continued for 3 min. The remaining half of the mixing water was added and the mixer was stirred at a speed of 300 r / min for 3 min to obtain the composite slurry. (4) Corrosion treatment and cutting of carbon fiber mesh: The cut carbon fiber mesh was placed in a mixture of 1 mol / L concentrated HNO3 and 2 mol / L concentrated H2SO4 and heat-treated at 60℃ for 2 h. After treatment, it was 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 plate. (5) Construction of the interface functional layer: The prepared composite slurry was brushed on the inner surface of the frame composed of the wall / board and the vertical partition plate. The coating thickness was controlled at 2~3 mm. Then, the carbon fiber mesh cut according to the surface size of the cement-based wall / board was glued on after corrosion treatment.

[0048] Interface functional layer 2 functions as the electrode material of the capacitor. The measured key performance indicators of interface functional layer 2 are: structural thickness of 2.46 mm, adhesive strength of 1.9 MPa, and areal capacitance of 617 F / m². 2 .

[0049] The raw material components of the energy storage and insulation layer 3, by weight, are: 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 the undisturbed red mud discharged from the Bayer process of aluminum electrolysis; the metakaolin is kaolin powder obtained by calcining at 750-850℃; the sodium silicate has a modulus of 1.2-1.5; the aluminum powder is foaming aluminum powder with a mesh size of 100-150 and an active aluminum content ≥98%; the foaming stabilizer is a compound of polycarboxylic acid mother liquor, polyacrylamide, sodium dodecylbenzene sulfonate, and polyethylene glycol-type alkyl acid polyoxyethylene ether, with a mass ratio of 1:0.45:0.3, and the solid content of the compounded foaming stabilizer is ≥40%.

[0050] The casting process of the energy storage insulation layer 3 includes the following steps: (1) Drying: Dry the original red mud at 80°C for 0.5-1h, and control the moisture content of the material after drying to be <2%; (2) Grinding: Grind and disperse the dried red mud using a ball mill for 5-10min, and control the particle size of the material after grinding to be ≤3% on a 45μm sieve; (3) Batching and mixing: Weigh red mud, metakaolin, and aluminum powder according to the proportion, add 70% mixing water, mix and stir them. Mix the mixture in a mixer at 300 rpm for 5 minutes to form a slurry mixture; then add sodium silicate, foaming stabilizer, potassium hydroxide, potassium chloride, iron oxide powder and 30% mixing water to the slurry, and continue mixing at 150~200 rpm for 3 minutes to form a foamed slurry; (4) Pouring foam: pour the mixed slurry into the grid space of the cement-based wall / board that has been constructed with the interface functional layer, with a pouring slurry mass of 31.3 kg / m 2 The pouring thickness is 90mm. After pouring, it needs to be covered and sealed for 3 days for curing. After curing, use a cutting machine to remove excess material along the top surface.

[0051] The measured key performance indicators of the energy storage insulation layer 3 are: bulk density 318 kg / m³ 3 It has a thermal conductivity of 0.0715 W / m·K, an ionic conductivity of 0.035 mS / cm, and a resistivity of 31.3 Ω·cm. It meets the requirements of being lightweight, heat-insulating, and energy-storing. In terms of heat insulation, it serves as an internal filler and heat insulation layer, and in terms of energy storage, it serves as an electrolyte component of a supercapacitor.

[0052] In this embodiment, the structure of the interface functional layer and the energy storage insulation layer are respectively produced using inorganic non-metallic composite materials of different components according to the above steps, forming an integrated building material for heat insulation and energy storage, with a storage energy density of 18.9 W·h / m³. 2 .

[0053] Example 3

[0054] 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, and has the function of an electrode material for a capacitor, providing 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 capacity, and also has energy storage function. The thickness of the energy storage insulation layer 3 is 100mm.

[0055] The cement-based wall / board 1 is a load-bearing structural layer of multifunctional building materials, with load-bearing function; vertical partition plates 6 should be set / installed on the surface of the cement-based wall / board 1, the vertical partition plates 6 divide the cement-based wall / board 1 into squares, each square is an energy storage unit, T-shaped metal embedded parts 7 and L-shaped metal embedded parts 8 need to be pre-embedded in the vertical partition plates 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 L-shaped metal embedded parts 8.

[0056] A method for preparing a cement-based integrated thermal insulation and energy storage building material includes the construction of an interface functional layer 2 and the pouring of an energy storage and thermal insulation layer 3.

[0057] The interface functional layer 2 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, by weight, are: 50 parts cementitious material; 40 parts porous ceramsite; 80 parts mixing water; 4 parts graphene nanosheets; and 200 parts dispersion. The cementitious material is 42.5 grade ordinary Portland cement. The porous ceramsite is shale ceramsite with a particle size ≤2mm and a bulk density of 0.82g / cm³. 3 The graphene nanosheets have a particle size D50 of 2.77 μm and a specific surface area of ​​650 m². 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 should have a thickness of 185μm and a mesh size of 0.3mm.

[0058] The construction process of the interface functional layer 2 includes the following steps: (1) Preparation of graphene nanosheet dispersion: Add graphene nanosheets to 50 parts by weight of dispersion and ultrasonically disperse for 2 hours to obtain graphene nanosheet dispersion; (2) Conductive aggregate treatment: Using porous ceramic particles as carrier, soak the ceramic particles in graphene nanosheet dispersion, and then transfer the dispersion to a stainless steel reactor for hydrothermal treatment at 160°C for 12 hours; after treatment, filter the ceramic particles and dry them in a 60°C forced-air drying oven for 2 hours to obtain conductive aggregate; (3) Preparation of composite slurry: Add the conductive aggregate to the remaining parts by weight of graphene The dispersion was moistened with half the weight of mixing water and placed in a mixer. The mixer was started at a speed of 100 r / min. During the mixing process, the cementitious material was slowly added. After the cementitious material was added, the mixer was continued for 3 min. The remaining half of the mixing water was added and the mixer was stirred at a speed of 300 r / min for 3 min to obtain the composite slurry. (4) Corrosion treatment and cutting of carbon fiber mesh: The cut carbon fiber mesh was placed in a mixture of 1 mol / L concentrated HNO3 and 2 mol / L concentrated H2SO4 and heat-treated at 60℃ for 2 h. After treatment, it was repeatedly rinsed with deionized water until neutral. Cut according to the inner surface dimensions of the frame composed of the wall / board and the vertical partition plate. (5) Construction of the interface functional layer: The prepared composite slurry was brushed on the inner surface of the frame composed of the wall / board and the vertical partition plate. The coating thickness was controlled at 2~3 mm. Then, the carbon fiber mesh cut according to the surface dimensions of the cement-based wall / board was glued on after corrosion treatment.

[0059] Interface functional layer 2 functions as the electrode material of the capacitor. The measured key performance indicators of interface functional layer 2 are: structural thickness of 2.93 mm, adhesive strength of 2.8 MPa, and areal capacitance of 852 F / m². 2 .

[0060] The raw material components of the energy storage and insulation layer 3, by weight, are: 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 the undisturbed red mud discharged from the Bayer process of aluminum electrolysis; the metakaolin is kaolin powder obtained by calcining at 750-850℃; the sodium silicate has a modulus of 1.2-1.5; the aluminum powder is foaming aluminum powder with a mesh size of 100-150 and an active aluminum content ≥98%; the foaming stabilizer is a compound of polycarboxylic acid mother liquor, polyacrylamide, sodium dodecylbenzene sulfonate, and polyethylene glycol-type alkyl acid polyoxyethylene ether, with a mass ratio of 1:0.4:0.3, and the solid content of the compounded foaming stabilizer is ≥40%.

[0061] The casting process of the energy storage and insulation layer 3 includes the following steps: (1) Drying: Dry the original red mud at a temperature of 80°C for 0.5-1h, and control the moisture content of the material after drying to be <2%; (2) Grinding: Grind and disperse the dried red mud using a ball mill for 5-10min, and control the particle size of the material after grinding to be ≤3% on a 45μm sieve; (3) Batching and mixing: Weigh the red mud, metakaolin, and aluminum powder according to the proportion, add 70% mixing water, mix them and stir. Mix at 300 rpm / min for 5 minutes to form a slurry mixture; then add sodium silicate, foaming stabilizer, potassium hydroxide, potassium chloride, iron oxide powder and 30% mixing water to the slurry, and continue mixing at 150~200 rpm / min for 3 minutes to form a foamed slurry; (4) Pouring foam: pour the mixed slurry into the grid space of the cement-based wall / board that has been constructed with the interface functional layer, with a pouring slurry mass of 31 kg / m 2 The pouring thickness is 100mm. After pouring, it needs to be covered and sealed for 3 days for curing. After curing, use a cutting machine to remove excess material along the top surface.

[0062] The measured key performance indicators of the energy storage insulation layer 3 are: bulk density 309 kg / m³ 3 It has a thermal conductivity of 0.0719 W / m·K, an ionic conductivity of 0.062 mS / cm, and a resistivity of 36.5 Ω·cm. It meets the requirements of being lightweight, heat-insulating, and energy-storing. In terms of heat insulation, it serves as an internal filler and heat insulation layer, and in terms of energy storage, it serves as an electrolyte component of a supercapacitor.

[0063] In this embodiment, the interface functional layer 2 and the energy storage and insulation layer 3 are manufactured using inorganic non-metallic composite materials of different components according to the above steps, forming an integrated building material for heat insulation and energy storage, with a storage energy density of 21.2 W·h / m³. 2 .

[0064] An upper surface layer 4 can be cast onto the energy storage and insulation layer 3 of the building material in this invention, serving as an encapsulation and protective layer for the building material. The exterior of the upper surface layer 4 is configured with external structural layers such as a surface functional layer and an energy storage control device 9, according to the building's usage requirements. Typical applications of the surface functional layer include decorative layers on the building's exterior surface / photovoltaic panels 5, etc. The energy storage control device 9 is the control and regulation unit for the building material's power storage; its circuit design and installation must be tailored to the overall building design and application scenario. Depending on the actual engineering situation, it can be assembled and installed in the factory using pre-embedded T-shaped metal parts 7 and L-shaped metal parts 8, or it can be installed on-site. This invention only relates to the design of the building material's composition, preparation process, and performance; it does not involve the application design of external structural layers such as surface functional layers for specific building forms.

[0065] The above embodiments are merely examples illustrating the explanation, specific implementation, and effects of the present invention, and are not intended to limit the invention. Based on this disclosure, some modifications or improvements without contributing any inventive step can be made, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of this disclosure fall within the scope of protection claimed in this disclosure.

Claims

1. A cement-based integrated thermal insulation and energy storage building material, characterized in that: 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 and functions as the electrode material of a capacitor, providing energy storage. The thickness of the interface functional layer is 2~3mm. The key performance indicators of the interface functional layer are: bonding strength ≥1MPa, and areal capacitance ≥500F / m². 2 The energy storage insulation layer is located above the interface functional layer, serving as the insulation layer of the building wall. It has good thermal insulation capabilities and also functions as an energy storage layer. The thickness of the energy storage insulation layer is 80~100mm, and its key performance indicators are: bulk density 300~350kg / m³. 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 as follows by weight: 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 insulation layer by weight are: 70-75 parts red mud, 20 parts metakaolin, 5 parts sodium silicate, 3-4 parts aluminum powder, 3-5 parts foaming stabilizer; 1-2 parts potassium hydroxide, 1-2 parts potassium chloride, 2-5 parts iron oxide powder, and 55-60 parts mixing water. Preparation of cement-based integrated thermal insulation and energy storage building materials, 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: Add graphene nanosheets to 50 parts by weight of dispersion and ultrasonically disperse for 2 hours to obtain graphene nanosheet dispersion; (2) Conductive aggregate treatment: Using porous ceramsite as a carrier, ceramsite is soaked in 4 parts by weight of graphene nanosheet dispersion, and then the dispersion is transferred to a stainless steel reactor and subjected to hydrothermal treatment at 160°C for 12 hours; after treatment, the ceramsite is filtered and dried in a 60°C forced-air drying oven for 2 hours to obtain conductive aggregate; (3) Preparation of composite slurry: Add the conductive aggregate to the remaining parts by weight of graphene dispersion, wet with half the parts by weight of mixing water, put it into a mixer, start stirring at 100r / 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 at a speed of 300 r / min for 3 minutes on the mixer to obtain the composite slurry; (4) Corrosion treatment and cutting of carbon fiber mesh: arrange the cut carbon fiber mesh in a mixture of 1 mol / L concentrated HNO3 and 2 mol / L concentrated H2SO4 and heat treat it at 60℃ for 2 hours; after treatment, rinse repeatedly with deionized water until neutral, and cut according to the inner surface size of the frame composed of the wall / board and the vertical partition plate; (5) Construction of interface functional layer: brush the prepared composite slurry on the inner surface of the frame composed of the wall / board and the vertical partition plate, and control the coating thickness to 2~3 mm, and then stick the carbon fiber mesh cut according to the surface size of the cement-based wall / board after corrosion treatment; The raw material processing and casting process of the energy storage insulation layer includes the following steps: (1) Drying: Dry the original red mud at 80℃ for 0.5-1h, and control the moisture content of the material after drying to <2%; (2) Grinding: Grind and disperse the dried red mud using a ball mill for 5-10min, and control the particle size of the material after grinding to ≤3% on a 45μm sieve; (3) Batching and mixing: Weigh red mud, metakaolin, and aluminum powder according to the proportion, add 70% mixing water, mix them and stir. Mix at 300 rpm / min for 5 minutes to form a slurry mixture; then add sodium silicate, foaming stabilizer, potassium hydroxide, potassium chloride, iron oxide powder and 30% mixing water to the slurry, and continue mixing at 150~200 rpm / min for 3 minutes to form a foamed slurry; (4) Pouring foam: pour the mixed slurry into the grid space of the cement-based wall / board that has been constructed with the interface functional layer, with a pouring slurry mass of 30~35 kg / m 2 .

2. The cement-based integrated thermal insulation and energy storage 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's cement-based walls / building panels. The cement-based walls / panels are the load-bearing structural layer of the multi-functional building materials, possessing load-bearing capabilities. Vertical partitions are installed on the surface of the cement-based walls / panels, dividing the surface into squares. The spaces within these squares are used to fill the interface functional layer and energy storage insulation layer materials. Each square is an energy storage unit. The vertical partitions are made of cement-based materials or other inorganic materials. T-shaped and L-shaped metal embedded parts are pre-embedded in the vertical partitions. The vertical partitions are anchored through the T-shaped and L-shaped metal embedded parts, and energy is transferred between the internal energy storage units and external control devices.

3. The cement-based integrated thermal insulation and energy storage building material according to claim 1, characterized in that: The cementitious material used is 42.5 grade ordinary Portland cement; the porous ceramsite used is shale ceramsite with a particle size ≤2mm and a bulk density ≤0.85g / cm³. 3 .

4. The cement-based integrated thermal insulation and energy storage building material according to claim 1, characterized in that: Graphene nanosheets should have a particle size D50 ≤ 3 μm, a thickness of 5~50 nm, and a specific surface area ≥ 600 m². 2 / g, thermal conductivity ≥3500w / m·K, electrical conductivity ≥100S / m.

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

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

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

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

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