Energy storage deicing building block brick based on industrial waste

Abstract

The invention belongs to the technical field of functional building materials, and particularly relates to an industrial waste-based energy storage and deicing building block brick, which comprises a cavity brick body, a brick cover arranged at the top of the cavity brick body, and a capacitor array arranged in a cavity of the cavity brick body, the cavity brick body is of a cuboid hollow structure, the top of the cavity brick body is open, the brick cover is a rectangular cover plate matched with the cavity brick body, the capacitor array comprises a plurality of capacitor monomers which are connected in series, and a separation diaphragm is arranged between every two adjacent capacitor monomers; each capacitor monomer comprises an anode electrode, an anode electrolyte, a diaphragm, a cathode electrolyte and a cathode electrode which are connected in sequence. The capacitor array is used as an energy storage unit to be integrated in the cavity of the cavity brick body, synchronous construction of energy storage and building block brick components is achieved through the cavity brick body-capacitor array-brick cover integrated structure, the system integration degree is high, the structure is compact, road paving and subsequent modular replacement and maintenance are facilitated, and the integrated energy storage and building block brick is suitable for application and popularization.

Description

Technical Field

[0001] This invention belongs to the field of functional building materials technology, specifically a storage and de-icing block brick based on industrial waste. Background Technology

[0002] In cold and freezing environments, areas such as sidewalks, tunnel entrances, and building exteriors are prone to icing and ice accumulation. Ice not only reduces the road surface adhesion coefficient and induces safety accidents such as pedestrians and vehicles skidding, but also causes blockages in parts such as bridge expansion joints and drainage structures, leading to frost heave damage and service performance degradation, which in turn leads to frequent emergency response and high maintenance costs.

[0003] Existing de-icing methods mainly include mechanical de-icing, application of de-icing agents, and external / electric heating de-icing. While mechanical de-icing can quickly remove surface ice and snow, it easily causes scratch damage to the road surface and waterproofing layer, and suffers from limited efficiency and re-icing problems. De-icing agents rely on chemical freezing point lowering mechanisms, and long-term use can lead to concrete salt damage and secondary environmental pollution, with their effectiveness significantly diminishing under extreme low-temperature conditions. External / electric heating de-icing can achieve active de-icing, but it usually requires laying independent heating cables or power supply facilities, resulting in complex system construction, high energy consumption, and susceptibility to problems such as localized overheating, circuit failure, and maintenance difficulties. More importantly, existing solutions often design "structural materials" and "power supply / de-icing systems" separately, with de-icing facilities often being externally mounted or attached as later-stage components. This makes it difficult to balance durability, maintainability, and cost control in large-area paving scenarios, forming a core bottleneck in de-icing engineering in cold regions—unstable energy sources, low system integration, and insufficient long-term service reliability.

[0004] The large amounts of fly ash / fly ash generated by industries such as thermal power and metallurgy are typical industrial wastes. Improper disposal can lead to environmental risks such as land occupation and dust dispersion. Alkali-activated cementitious materials based on fly ash / fly ash offer a low-carbon potential pathway for the resource utilization of solid waste. However, most existing fly ash-based masonry blocks focus on load-bearing, thermal insulation, or durability modification, remaining at the single-function level of "structural materials." Even those few studies that attempt to endow fly ash-based masonry blocks with electrical conductivity or thermal management capabilities mostly rely on the addition of conductive fillers or the application of external heating layers. This results in problems such as discontinuous conductive networks, interface peeling, performance drift under wet freeze-thaw conditions, and vulnerability of external cables, making it difficult to meet the long-term stable operation requirements under repeated freeze-thaw cycles and superimposed loads in cold regions.

[0005] Therefore, there is an urgent need for a new type of functional building material for engineering applications in cold regions, which can deeply couple the high-value utilization of industrial waste with energy storage and de-icing functions without significantly increasing the complexity of construction, and solve the problems of easy damage and difficult maintenance of external systems through structured encapsulation and reliable electrical connection. Summary of the Invention

[0006] To address the above problems, this invention provides an energy storage and de-icing block brick based on industrial waste. The block brick uses fly ash as the main solid raw material and is prepared into a brick substrate using an alkaline activation system composed of sodium hydroxide solution and sodium silicate solution. A capacitor array composed of fly ash-based electrodes and gel electrolyte is integrated into the cavity of the brick substrate to realize the energy storage and de-icing applications of the block brick, taking into account both the resource utilization of solid waste and the low-carbon and sustainable attributes.

[0007] This invention is specifically achieved through the following technical solution: An energy storage and de-icing block brick based on industrial waste, comprising a hollow brick body, a brick cover disposed on top of the hollow brick body, and a capacitor array disposed within the cavity of the hollow brick body; the hollow brick body is a rectangular hollow structure with an open top and an internal rectangular cavity; the brick cover is a rectangular cover plate, adapted to the hollow brick body and bonded together; the capacitor array comprises multiple capacitor cells connected in series, with a separator between each pair of adjacent capacitor cells; each capacitor cell comprises, from left to right, an anode electrode, an anode electrolyte, a separator, a cathode electrolyte, and a cathode electrode, with titanium wires leading out from the anode and cathode electrodes as connecting parts; the gap between the hollow brick body and the capacitor cells is filled and encapsulated with photocurable resin.

[0008] The aforementioned energy storage and de-icing block brick based on industrial waste has an external length, width, and height of 240mm, 115mm, and 40mm for the hollow brick body, and a cavity length, width, and height of 137mm, 23mm, and 25mm for the hollow brick body. The brick cover has a length, width, and height of 240mm, 115mm, and 13mm for the hollow brick body and the brick cover. After assembly, the length, width, and height of the whole brick are 240mm, 115mm, and 53mm for the hollow brick body and the brick cover.

[0009] The aforementioned energy storage and de-icing block brick based on industrial waste has a capacitor array inside the hollow brick body comprising 5 capacitor cells connected in series. The overall length, width, and height of each capacitor cell are 25mm, 23mm, and 25mm, respectively, and the thickness of the separation diaphragm is 3mm.

[0010] The aforementioned energy storage and de-icing block bricks based on industrial waste use polypropylene membranes with a thickness of 3 mm for both the separation diaphragm and the diaphragm.

[0011] The aforementioned energy storage and de-icing block bricks based on industrial waste, wherein the anode and cathode electrodes are made of identical materials and have the same structure, are collectively referred to as electrode A. The preparation method of electrode A includes: (1) Sodium hydroxide solution and sodium silicate solution are mixed at a mass ratio of 2:15 to obtain mixture A; the concentration of sodium hydroxide solution is 320 g / L, and the mass fraction of SiO2 in sodium silicate solution is 8.0% and the mass fraction of Na2O is 26.8%; (2) Mix the mixture A obtained in step (1) with fly ash at a mass ratio of 1:2, and stir the mixture at high speed until it is uniformly mixed to obtain mixture B; (3) Pour mixture B into the electrode mold and shake for 2-5 minutes to remove air bubbles. The center of the top end face of the electrode mold has an opening for inserting titanium wire. After removing air bubbles, insert a titanium wire vertically into the mold from the opening at the top of the electrode mold as the connection part of the electrode. The titanium wire extends 70-100 mm out of the top of the electrode mold. Then cure at 60℃ for 72 hours. After demolding, the electrode blank is obtained. (4) Polish the electrode blank obtained in step (3) with sandpaper, wash it several times with distilled water to remove surface dust, and then dry it at 160℃ for 1-2 hours to obtain the electrode sample. (5) Place the electrode sample into a high-pressure reactor, add 3,4-ethylenedioxythiophene and hydrochloric acid, seal the high-pressure reactor and place it in an oven at 155°C for 15-20 h; after completion, wash the obtained product with methanol 3-5 times and then dry it at room temperature to obtain electrode A.

[0012] Further, in step (3), the length, width, and height of the inner cavity of the electrode mold are 25mm, 5mm, and 25mm respectively, and the top size of the electrode mold is 25mm×5mm. After demolding, an electrode blank with length, width, and height of 25mm, 5mm, and 25mm is obtained. In step (5), the concentration of 3,4-ethylenedioxythiophene is 0.85M and the volume used is 800μL. The concentration of hydrochloric acid is 12M and the volume used is 1600μL.

[0013] The aforementioned energy storage and de-icing blocks based on industrial waste contain anolyte and cathode electrolytes of identical material and structure, both being gel electrolytes, which are prepared according to the following method: Polyvinyl alcohol was dissolved in 1M H2SO4 solution at 80°C with stirring. The mass ratio of polyvinyl alcohol to H2SO4 solution was 3g:20mL. The mixture was stirred for 1 hour to obtain a mixed solution. The mixed solution was poured into a mold with an inner cavity length, width, and height of 25mm, 5mm, and 25mm, respectively. The mold and the mixed solution inside the mold were placed in an environment of -20°C for 30 minutes, and then removed and placed at room temperature for 30 minutes. This was repeated as one cycle. Three cycles were repeated in this manner, with each cycle lasting 1 hour. After demolding, a gel electrolyte with a length, width, and height of 25mm, 5mm, and 25mm was obtained.

[0014] The aforementioned energy storage and de-icing block bricks based on industrial waste, wherein the method for preparing the hollow brick body and the brick cover includes: (1) Sodium hydroxide solution and sodium silicate solution are mixed at a mass ratio of 2:15 to obtain mixture A; the concentration of sodium hydroxide solution is 320 g / L, and the mass fraction of SiO2 in sodium silicate solution is 8.0% and the mass fraction of Na2O is 26.8%; (2) Mix the mixture A obtained in step (1) with fly ash at a mass ratio of 1:2, and stir the mixture at high speed until it is uniformly mixed to obtain mixture B; (3) Pour the mixture B into the cavity brick mold and the brick cover mold respectively, shake for 2-5 minutes to remove air bubbles, and then cure the cavity brick mold and the mixture B inside it, and the brick cover mold and the mixture B inside it at 60°C for 72-80 hours. After demolding, the cavity brick and the brick cover are obtained.

[0015] The aforementioned energy storage de-icing block brick based on industrial waste is assembled as follows: Assembled capacitor cells are placed into the cavities of a hollow brick body. Five capacitor cells are placed side-by-side in each cavity of the hollow brick body to form a capacitor array. A polypropylene diaphragm is placed between adjacent capacitor cells as a separation diaphragm. Titanium wires between adjacent capacitor cells are connected using wires. The titanium wire on the anode electrode of the preceding capacitor cell is connected to the titanium wire on the cathode electrode of the adjacent capacitor cell. Titanium wires on the cathode electrode and anode electrode are left exposed at the two ends of the capacitor cell. These two exposed titanium wires are bent and led out from the top of the hollow brick body for further connection to a solar integrated circuit. The gap between the hollow brick body and the capacitor cells is filled with photocurable resin. A brick cover is placed on top of the hollow brick body, and the brick cover is fixed to the hollow brick body with epoxy resin to complete the encapsulation, thus obtaining the energy storage de-icing block brick.

[0016] Compared with the prior art, the present invention has significant advantages and beneficial effects, achieving considerable technological progress and practicality, and has broad application value. It possesses at least the following advantages: (1) The energy storage and de-icing block bricks based on industrial waste use fly ash / fly ash as the main raw material and are prepared by an alkaline activation system of sodium hydroxide solution and sodium silicate solution. Compared with traditional block bricks based on cement clinker, it can effectively improve the utilization level of industrial waste and has the advantages of resource utilization of building materials and low-carbon sustainability.

[0017] (2) The present invention creatively integrates the capacitor array as an energy storage unit into the cavity of the hollow brick body. Through the integrated structure of "hollow brick body-capacitor array-brick cover", the energy storage and the block components are constructed simultaneously. Compared with the existing external heating or external energy storage / conductive layer solutions, the system has a high degree of integration and a compact structure, which is convenient for road paving and subsequent modular replacement and maintenance.

[0018] (3) This invention obtains anode and cathode electrodes by cleaning and polishing the electrode blanks, reacting them with 3,4-ethylenedioxythiophene and hydrochloric acid in a high-pressure reactor, and then washing and drying them with methanol to form a stable conductive active layer on the electrode surface. This significantly enhances the functionality of the electrodes and provides key support for the "energy storage and discharge" function of the energy storage and de-icing blocks. During the forming and curing process of the electrode blanks, titanium wires are pre-embedded as connecting parts. The titanium wires extend 70-100mm beyond the electrode end face, enabling reliable conduction and low-resistance connection between the electrodes and external circuits. Compared with later bonding wires or surface clamping connection methods, the connection stability of this invention is higher and the assembly consistency is better, which can effectively reduce energy loss and failure risk caused by poor contact.

[0019] (4) This invention uses a PVA-sulfuric acid system to prepare a gel electrolyte preform and prepares an anode / cathode gel electrolyte through three cycles of alternating freeze-thaw cycles at -20℃ and room temperature. The resulting gel electrolyte can fully adhere to the contact surface of the anode or cathode electrode and maintain a stable morphology. Compared with the liquid electrolyte solution, it has the characteristics of being less prone to leakage, easy to encapsulate, and having stable interface contact, which can effectively improve the reliability of capacitor assembly and the integrated safety of the energy storage de-icing block bricks.

[0020] (5) In the process of assembling capacitor cells, the present invention uses a polypropylene diaphragm to isolate the cathode and anode, and uses a separation diaphragm to isolate adjacent capacitor cells in the cavity of the energy storage de-icing block brick. At the same time, the gap between the cavity brick and the capacitor is filled with light-cured resin and encapsulated as a whole, forming multiple short circuit protection and structural curing protection. Compared with the integrated method that lacks isolation and encapsulation, it can effectively reduce the risk of internal short circuit and improve the long-term service stability and engineering safety.

[0021] (6) In this invention, multiple capacitor cells in the cavity of the hollow brick body are connected in series with titanium metal wires and the connection part is led out from the side of the energy storage and de-icing block brick. It can be directly used to connect the solar integrated circuit and supply energy to the energy storage and de-icing block brick through the solar integrated circuit, realizing the unified interface of "energy collection-energy storage-energy supply". Compared with the system that requires additional conversion or complex wiring, it has the advantages of simple connection, strong scalability and adaptability to field integration, which makes it easy to promote and apply. Attached Figure Description

[0022] Figure 1This is an exploded schematic diagram of the energy storage and de-icing block brick of the present invention.

[0023] Figure 2 This is a schematic diagram of the structure of a single capacitor cell.

[0024] Figure 3 This is a schematic diagram of five individual capacitors connected in series.

[0025] Figure 4 This is a CV curve test diagram of the capacitor cell prepared in Example 4.

[0026] Figure 5 This is a GCD curve test diagram of the capacitor cell prepared in Example 4.

[0027] Figure 6 This is a Nyquist curve test diagram of the capacitor cell prepared in Example 4.

[0028] Figure 7 This is a test graph of the cyclic stability of the capacitor cell prepared in Example 4.

[0029] Figure 8 The graph shows the charge and discharge performance test results of a capacitor array obtained by connecting five capacitor cells prepared in Example 4 in series.

[0030] Figure 9 The results are the compressive strength test results of the energy storage de-icing block bricks prepared in Example 5.

[0031] Figure 10 It is a curve showing the change in surface temperature of the energy storage de-icing block bricks over time during the de-icing process.

[0032] Figure 11 It is a curve showing the change in the residual ice mass of the energy storage de-icing bricks over time during the de-icing process.

[0033] In the diagram: 1-Hollow brick body; 2-Brick cover; 3-Capacitor cell; 4-Separation diaphragm; 5-Anode electrode; 6-Anode electrolyte; 7-Diaphragm; 8-Cathode electrolyte; 9-Cathode electrode; 10-Titanium wire; 11-Wire. Detailed Implementation

[0034] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0035] like Figure 1As shown, the present invention provides an energy storage and de-icing block brick based on industrial waste, comprising a hollow brick body 1, a brick cover 2 disposed on the top of the hollow brick body 1, and a capacitor array disposed within the cavity of the hollow brick body 1. Figure 1 As shown, the hollow brick body 1 is a rectangular hollow structure with an open top and a rectangular cavity inside; the brick cover 2 is a rectangular cover plate that fits the hollow brick body 1 and is bonded and fixed between them; the capacitor array includes multiple capacitor cells 3 connected in series, and a separation diaphragm 4 is provided between each two adjacent capacitor cells 3 to prevent short circuits; the gap between the hollow brick body 1 and the capacitor cells 3 is filled with light-cured resin and encapsulated.

[0036] In a preferred embodiment, the hollow brick body 1 has a length, width, and height of 240mm, 115mm, and 40mm, respectively, and its cavity has a length, width, and height of 137mm, 23mm, and 25mm, respectively; the brick cover 2 has a length, width, and height of 240mm, 115mm, and 13mm, respectively. After assembling the hollow brick body 1 and the brick cover 2, the overall brick has a length, width, and height of 240mm, 115mm, and 53mm, which is consistent with the dimensions of existing standard building bricks, facilitating large-scale use.

[0037] Furthermore, in Figure 1 In the embodiment shown, the capacitor array inside the cavity brick 1 includes 5 capacitor cells 3 connected in series. The overall length, width and height of the capacitor cells 3 are 25mm, 23mm and 25mm respectively. The thickness of the separation diaphragm 4 is 3mm. A total of 4 separation diaphragms 4 are arranged between the 5 capacitor cells 3 connected in series.

[0038] In one embodiment, the separating diaphragm 4 is a polypropylene diaphragm with a length, width and thickness of 25 mm, 23 mm and 3 mm, respectively.

[0039] The above description is merely one embodiment of the present invention and should not be considered as a limitation thereof.

[0040] like Figure 2 As shown, the capacitor cell 3 includes an anode electrode 5, an anode electrolyte 6, a diaphragm 7, a cathode electrolyte 8, and a cathode electrode 9 connected sequentially from left to right. Titanium wires 10 are led out from the anode electrode 5 and the cathode electrode 9 as connecting parts.

[0041] Furthermore, the anode electrode 5 and the cathode electrode 9 are made of identical materials and have the same structure. For ease of description, they will be referred to as "electrode A" below. Electrode A is prepared according to the following method: (1) Sodium hydroxide solution and sodium silicate solution are mixed at a mass ratio of 2:15 to obtain mixture A; wherein, the concentration of sodium hydroxide solution is 320 g / L (obtained by dissolving 320 g of analytical grade sodium hydroxide in 1 L of deionized water), and the mass fraction of SiO2 in sodium silicate solution is 8.0% and the mass fraction of Na2O is 26.8%; (2) Mix the mixture A obtained in step (1) with fly ash at a mass ratio of 1:2, and stir the mixture at high speed for 3-10 minutes until it is uniformly mixed to obtain mixture B; (3) Pour mixture B into the electrode mold and shake for 2 minutes to remove air bubbles. The inner cavity of the electrode mold has a length, width, and height of 25 mm, 5 mm, and 25 mm, respectively. The top of the electrode mold has a size of 25 mm × 5 mm. An opening is provided at the center of the top end face of the electrode mold for inserting titanium wire 10. After removing air bubbles, insert a titanium wire 10 with a diameter of 0.2 mm vertically into the mold from the opening on the top end face of the electrode mold to serve as the connection part of the electrode. The length of the titanium wire 10 is 100-150 mm, and the titanium wire 10 extends 70-100 mm beyond the top of the electrode mold. Then, cure at 60°C for 72 hours. After demolding, an electrode blank with a length, width, and height of 25 mm, 5 mm, and 25 mm is obtained. (4) Polish the electrode blank obtained by curing in step (3) with sandpaper, wash it with distilled water 3-5 times to remove surface dust, and then dry it at 160℃ for 1-2 hours to obtain the electrode sample. (5) Place the electrode sample into a high-pressure reactor, add 800 μL of 0.85 M 3,4-ethylenedioxythiophene and 1600 μL of 12 M hydrochloric acid, seal the high-pressure reactor and place it in an oven at 155 °C for 15-20 h; after completion, wash the obtained product with methanol several times (3-5 times) to remove impurities, residual hydrochloric acid and unreacted 3,4-ethylenedioxythiophene, and then dry it at room temperature to obtain the electrode A.

[0042] The anolyte 6 and the cathode electrolyte 8 are identical in material and structure, both being gel electrolytes, which are prepared according to the following method: PVA (polyvinyl alcohol) was dissolved in 1M H2SO4 solution at 80°C with stirring. The mixture was stirred for 1 hour to obtain a mixed solution. The mixed solution was poured into a mold with an inner cavity length, width, and height of 25 mm, 5 mm, and 25 mm, respectively. The mold and the mixed solution inside the mold were placed in an environment of -20°C for 30 minutes, and then removed and placed at room temperature for 30 minutes. This was repeated as one cycle. Three cycles were repeated in this manner, each cycle lasting 1 hour. After demolding, the gel electrolyte was obtained.

[0043] Preferably, the mass ratio of PVA to the volume ratio of 1M H2SO4 solution is 3g:20mL.

[0044] Electrode A and gel electrolyte were prepared according to the above method. Two electrodes A (one as anode electrode 5, the other as cathode electrode 9), two gel electrolytes (one as anode electrolyte 6, the other as cathode electrolyte 8), and a separator 7 were assembled into a single capacitor model in the following order from left to right: anode electrode 5, anode electrolyte 6, separator 7, cathode electrolyte 8, and cathode electrode 9. A 3mm thick polypropylene separator 7 was used to effectively prevent short circuits. The length, width, and height of separator 7 could be 25mm, 3mm, and 25mm, respectively. The assembled single capacitor model was placed in a vacuum dryer for 5-10 minutes to promote degassing and bonding at the interface, achieving preliminary shaping and improving the interface stability of the capacitor assembly. The final result was a single capacitor unit 3 with overall length, width, and height dimensions of 25mm, 23mm, and 25mm, respectively. When assembling the single capacitor model, it was necessary to ensure that the exposed titanium wires 10 on the anode electrode 5 and cathode electrode 9 were aligned.

[0045] The prepared capacitor cells 3 are placed into the cavities of the hollow brick body 1. Five capacitor cells 3 connected in series are placed side-by-side in each cavity of the hollow brick body 1 to form a capacitor array. A polypropylene diaphragm 25mm long, 23mm wide, and 3mm thick is placed between adjacent capacitor cells 3 as a separation diaphragm 4 to prevent short circuits. The titanium wires 10 between adjacent capacitor cells 3 are connected using wires 11 (titanium wires can be used). The titanium wire 10 on the anode electrode of the preceding capacitor cell is connected to the titanium wire 10 on the cathode electrode of the adjacent capacitor cell. The capacitor cells 3 at both ends have titanium wires 10 on the cathode electrode 9 and the anode electrode 5 respectively. Figure 3 As shown, the two titanium wires 10 that are left out are bent out from the top of the hollow brick body 1 for further connection of the solar integrated circuit. The gap between the hollow brick body 1 and the capacitor cell 3 is filled with photocurable resin, and the brick cover 2 is placed on top of the hollow brick body 1. The brick cover 2 and the hollow brick body 1 are fixed with epoxy resin to complete the encapsulation.

[0046] The hollow brick body 1 and the brick cover 2 can be prepared according to the following method: The mixture B was prepared according to the aforementioned method for preparing electrode A. The mixture B was poured into the mold of the hollow brick body 1 and the mold of the brick cover 2, respectively, and shaken for 2-5 minutes to remove air bubbles. Then, the mold of the hollow brick body 1 and the mixture B inside it, and the mold of the brick cover 2 and the mixture B inside it were cured at 60°C for 72-80 hours. After demolding, the hollow brick body 1 and the brick cover 2 were obtained. The hollow brick body 1 is a rectangular hollow structure with an open top and a rectangular cavity inside. The outer length, width and height of the hollow brick body 1 are 240mm, 115mm and 40mm respectively, and the length, width and height of its cavity are 137mm, 23mm and 25mm respectively. The brick cover 2 is a rectangular cover plate with a length, width and height of 240mm, 115mm and 13mm respectively. After the hollow brick body 1 and the brick cover 2 are assembled, the length, width and height of the whole brick are 240mm, 115mm and 53mm respectively.

[0047] The present invention will be described in detail below with reference to specific embodiments. Unless otherwise specified, all conditions in the embodiments are performed under conventional conditions or conditions recommended by the manufacturer. Raw materials and reagents whose manufacturers are not specified are all commercially available products.

[0048] Example 1 The methods for preparing hollow brick bodies and brick covers include: (1) Sodium hydroxide solution and sodium silicate solution are mixed at a mass ratio of 2:15 to obtain mixture A; wherein, the concentration of sodium hydroxide solution is 320 g / L (obtained by dissolving 320 g of analytical grade sodium hydroxide in 1 L of deionized water, and the ratio can be increased), and the mass fraction of SiO2 in sodium silicate solution is 8.0% and the mass fraction of Na2O is 26.8%; (2) Mix the mixture A obtained in step (1) with fly ash at a mass ratio of 1:2, and stir the mixture at high speed for 3 minutes to obtain mixture B; (3) Pour mixture B into the cavity brick mold and the brick cover mold respectively, shake for 2-5 minutes to remove air bubbles, and then cure the cavity brick mold and the mixture B inside it, and the brick cover mold and the mixture B inside it at 60°C for 72 hours. After demolding, cavity brick and brick cover are obtained respectively. The cavity brick is a rectangular hollow structure with an open top and a rectangular cavity inside. The external length, width and height of the cavity brick are 240mm, 115mm and 40mm respectively, and the length, width and height of the cavity are 137mm, 23mm and 25mm respectively. The brick cover is a rectangular cover plate with a length, width and height of 240mm, 115mm and 13mm respectively.

[0049] Example 2 The anode and cathode electrodes are prepared with identical materials and structures, and are collectively referred to as "electrode A". The preparation methods for electrode A include: (1) Prepare mixture B according to steps (1) and (2) of Example 1; (2) Pour mixture B into the electrode mold and shake for 2-5 minutes to remove air bubbles. The inner cavity of the electrode mold has a length, width, and height of 25 mm, 5 mm, and 25 mm, respectively. The top of the electrode mold has a size of 25 mm × 5 mm. An opening is provided at the center of the top end face for inserting a titanium wire. After removing air bubbles, insert a titanium wire with a diameter of 0.2 mm vertically into the mold from the opening at the top of the electrode mold as the connection part of the electrode. The length of the titanium wire is 120 mm and the titanium wire extends 100 mm beyond the top of the electrode mold. Then, cure at 60°C for 72 hours. After demolding, an electrode blank with a length, width, and height of 25 mm, 5 mm, and 25 mm is obtained. (3) Polish the electrode blank obtained in step (2) with sandpaper, wash it several times with distilled water to remove surface dust, and then dry it at 160°C for 1 hour to obtain the electrode sample. (4) Place the electrode sample into a high-pressure reactor, add 800 μL of 0.85 M 3,4-ethylenedioxythiophene and 1600 μL of 12 M hydrochloric acid, seal the high-pressure reactor and place it in an oven at 155 °C for 15 h; after completion, wash the obtained product several times with methanol to remove impurities, residual hydrochloric acid and unreacted 3,4-ethylenedioxythiophene, and then dry it at room temperature to obtain electrode A with length, width and height of 25 mm, 5 mm and 25 mm respectively.

[0050] Example 3 Preparation of gel electrolytes, including: PVA was dissolved in 1M H2SO4 solution at 80°C with stirring. The mass ratio of PVA to the volume of 1M H2SO4 solution was 3g:20mL. The mixture was stirred for 1 hour to obtain a mixed solution. The mixed solution was poured into a mold with an inner cavity length, width, and height of 25mm, 5mm, and 25mm, respectively. The mold and the mixed solution inside the mold were placed in an environment of -20°C for 30 minutes, and then removed and placed at room temperature for 30 minutes. This was repeated as one cycle. Three cycles were repeated in this manner, with each cycle lasting 1 hour. After demolding, a gel electrolyte with a length, width, and height of 25mm, 5mm, and 25mm was obtained.

[0051] Example 4 Methods for assembling capacitor cells include: Two electrodes A prepared in Example 2 were used, one as the anode electrode and the other as the cathode electrode. Two gel electrolytes prepared in Example 3 were also used, one as the anode electrolyte and the other as the cathode electrolyte. A polypropylene diaphragm was cut to a length, width, and thickness of 25 mm, 25 mm, and 3 mm, respectively. A single capacitor model was assembled in the order of anode electrode, anode electrolyte, diaphragm, cathode electrolyte, and cathode electrode. The assembled single capacitor model was placed in a vacuum desiccator and dried for 6 minutes to promote degassing and bonding at the interfaces, achieve preliminary shaping, and improve the interface stability of the capacitor assembly. The final capacitor unit had overall length, width, and height dimensions of 25 mm, 23 mm, and 25 mm, respectively. When assembling the single capacitor model, it was ensured that the exposed titanium wires on the anode and cathode electrodes were aligned.

[0052] Example 5 The method for assembling energy storage de-icing blocks includes: The capacitor cells assembled in Example 4 are placed into the cavities of the hollow bricks prepared in Example 1. Five capacitor cells assembled in Example 4 are placed side-by-side in each cavity of the hollow brick to form a capacitor array. A 25mm long, 23mm wide, and 3mm thick polypropylene diaphragm is placed between adjacent capacitor cells as a separation diaphragm to prevent short circuits. Titanium wires (which can be titanium wires) are used to connect the titanium wires between adjacent capacitor cells. The titanium wire on the anode electrode of the preceding capacitor cell is connected to the titanium wire on the cathode electrode of the adjacent capacitor cell. Titanium wires on the cathode and anode electrodes are left exposed at the two ends of the capacitor cells, respectively. These two exposed titanium wires are bent and led out from the top of the hollow brick for further connection to the solar integrated circuit. The gaps between the hollow brick and the capacitor cells are filled with photocurable resin. A brick cover is placed on top of the hollow brick, and the brick cover is fixed to the hollow brick with epoxy resin to complete the encapsulation, resulting in an energy storage de-icing block brick.

[0053] The anode and cathode titanium wires of the capacitor cell prepared in Example 4 were connected to the anode and cathode of an electrochemical workstation, respectively. The CV curves of the capacitor cell were tested, with a scan voltage of 0-1.0 V and scan rates of 20 mV / s, 50 mV / s, and 100 mV / s. Data were collected after the current response stabilized. Figure 4 The CV curves shown are nearly rectangular in shape, and the forward and reverse scans are basically symmetrical, indicating that the energy storage units corresponding to this dataset are mainly capacitor-type energy storage.

[0054] The GCD curve of the capacitor cell prepared in Example 4 was tested by constant current charging and discharging within a voltage window of 0-1.0 V, with charging and discharging currents of 0.05 A, 0.1 A, and 0.2 A, respectively. The voltage-time curves were recorded to obtain... Figure 5 The GCD curve shown. It can be seen that... Figure 5 All three sets of curves exhibit near-linear triangular discharge characteristics (after deducting the initial instantaneous voltage drop), which is a typical capacitor discharge mode. The initial voltage drop (IR drop) reflects an equivalent series resistance (ESR) of approximately 1.29-1.34 Ω (close to each other in all three sets). This indicates that the capacitor cell prepared in Example 4 has stable internal resistance and good discharge curve repeatability. The capacitor cell can still discharge stably at higher currents, demonstrating its potential to provide energy to the load. Simultaneously, the presence of the equivalent series resistance (ESR) means that some energy will be dissipated as heat, which can be converted into a beneficial Joule heating contribution in the "de-icing" scenario.

[0055] The capacitor cells prepared in Example 4 were tested using the EIS test method. An AC disturbance with an amplitude of 5mV and a frequency range of 0.01-10 was applied at open-circuit voltage (OCV). 5 Hz, to obtain Figure 6 The Nyquist curves are shown. It can be seen that the real intercept (minimum Z′) at the high-frequency end is approximately 1.09 Ω, which can be used to characterize the system's overall ohmic terms, including solution resistance and current collector contact resistance. As the frequency decreases, Z′ gradually increases, and -Z″ also increases, exhibiting a sloping trend at the low-frequency end that approximates the Warburg diffusion characteristic. The capacitor cells exhibit relatively stable ohmic impedance, and the diffusion behavior of ions in the porous structure can be observed, indicating the existence of a working ion transport channel in the electrode / gel electrolyte system; the impedance spectrum characteristics are consistent with the capacitive behavior of CV and GCD.

[0056] Figure 7 This is a cycle stability test chart of the capacitor cell prepared in Example 4. Under constant current of 0.10 A and voltage window of 0-1.0 V, it underwent 5000 continuous charge-discharge cycles. The capacitance retention rate and coulombic efficiency were calculated based on the discharge stage. The capacitance retention rate gradually decreased from 100% to approximately 91.91% at 5000 cycles. While there was some structural / interface fine-tuning or a small amount of irreversible loss during long-term cycling, the attenuation was not significant, indicating that the capacitor cell prepared in Example 4 possesses good cycle stability and reversibility.

[0057] Five capacitor cells prepared in Example 4 were connected in series with titanium wire to form a capacitor array. The anode and cathode of the array were connected to the anode and cathode of an electrochemical workstation, respectively. The charge-discharge performance was tested by charging to approximately 5.0 V with a constant current of 0.10 A, and then discharging to the cutoff voltage of 0 V with a constant current of 0.10 A. The voltage-time curves were recorded to obtain... Figure 8The charging and discharging performance test graph is shown. It can be seen that the initial voltage of the five capacitor cells connected in series is about 5.01 V, the discharge time is about 150 s (0.1 A), and the curve still maintains the linear discharge characteristics of the capacitor, indicating that the capacitor energy storage array has high-end voltage output capability, which is convenient for field deployment and external modular circuits.

[0058] Figure 9 The results show the compressive strength test results of the energy storage de-icing brick blocks prepared in Example 5. Six energy storage de-icing brick block samples were prepared according to the methods of Examples 1-5, labeled S1, S2, S3, S4, S5, and S6. Uniaxial compression loading was performed using an electronic universal testing machine, with the force applied to the maximum surface of the energy storage de-icing brick block. The loading method was displacement control, with a speed of 1 mm / min. The peak failure load was recorded and converted into compressive strength. The compressive strength range of the six energy storage de-icing brick block samples was 30.51-34.02 MPa, with an average of approximately 32.43 MPa and a standard deviation of approximately 1.24 MPa. The dispersion was small, indicating good consistency among the six energy storage de-icing brick block samples.

[0059] Figure 10 This is a curve showing the change in surface temperature of the energy storage de-icing block bricks over time during the de-icing process. The energy storage de-icing block bricks prepared in Example 5 were placed in a low-temperature test chamber, with the ambient temperature set to -8 to -10 ℃ (compared to...). Figure 10 The initial temperature was consistent (approximately -8.2 ℃). The surface temperature of the energy storage de-icing block bricks was measured using a T-type surface thermocouple and stabilized for 30 minutes. Water spraying was then used to ensure an ice thickness of at least 2 mm on the surface. The anode and cathode titanium wires from the energy storage de-icing block bricks were connected to the positive and negative terminals of an adjustable DC regulated power supply, respectively. With the power-on mode activated, the initial temperature of the energy storage de-icing block bricks was approximately -8.2 ℃. As the power-on time increased, the temperature of the energy storage de-icing block bricks rose, reaching a peak temperature (approximately 2.96 ℃) after about 12 minutes. Subsequently, the temperature of the energy storage de-icing block bricks decreased, exhibiting a "rise then fall" trend, consistent with the following sequence: heat generation during the discharge phase → reaching peak temperature → cooling down after energy depletion or heat dissipation becoming dominant. The energy storage de-icing block bricks not only raise the temperature above the phase transition temperature of ice but also maintain this temperature for a certain duration, which is beneficial for weakening ice-substrate adhesion and promoting melting.

[0060] Figure 11 This is a curve showing the change in residual ice mass of the energy storage de-icing bricks over time during the de-icing process. The energy storage de-icing bricks prepared in Example 5 were placed in a low-temperature test chamber, with the ambient temperature set to -8 to -10 ℃ (compared to...). Figure 10The initial temperature was consistent (measured at approximately -8.2 ℃). The surface temperature of the energy storage de-icing block bricks was measured using a T-type surface thermocouple and stabilized for 30 minutes. Water spraying and other methods were then used to ensure the ice thickness on the upper surface was no less than 2 mm. Before power-on, the initial ice mass of the energy storage de-icing block bricks was calculated to be approximately 119.8 g using the difference method. The anode and cathode titanium wires from the energy storage de-icing block bricks were connected to the positive and negative terminals of an adjustable DC regulated power supply, respectively. After power-on, the ice mass of the energy storage de-icing block bricks decreased rapidly, dropping to below 50% of the initial value in about 7 minutes, and approaching 0 g by 12 minutes. During the period from 5 to 14 minutes, the surface temperature of the energy storage de-icing block bricks remained above 0 ℃ (see...). Figure 10 This corresponds significantly to the rapid decrease in ice mass within 0-12 minutes: once the surface temperature crosses the phase transition threshold and remains so, the melting rate accelerates significantly.

[0061] In summary, from Figure 4 and Figure 5 It can be seen that the capacitor cell exhibits typical capacitive reversible charge and discharge characteristics. The current response increases with the increase of the scan rate and the curve is symmetrical. The constant current discharge curve is nearly linear and remains stable under different currents. Figure 6 The capacitor cell exhibits a relatively stable ohmic impedance and a certain diffusion impedance characteristic, consistent with its capacitive behavior. Figure 7 In the cyclic stability test, the capacitance retention rate of individual capacitors decreased slowly with the number of cycles, while the coulombic efficiency remained at a high level, indicating that the individual capacitors are usable for repeated charging and discharging. In the charge-discharge test of a capacitor array formed by five capacitors connected in series, the output voltage was significantly increased and a controllable discharge process was maintained, meeting the voltage matching requirements with external integrated circuits. Furthermore, the compressive strength of the energy storage de-icing block bricks remained stable, indicating that the structural load-bearing performance meets the basic requirements for component application. In the de-icing demonstration of the energy storage de-icing block bricks, the surface temperature rapidly rose from negative to above 0°C and remained there for a certain period, while the ice mass on the brick surface rapidly decreased over time and approached zero, verifying the functional realization path of the energy storage de-icing block bricks' "energy storage-power supply-de-icing" function. The above experiments verified the rapid de-icing capability of the energy storage de-icing block bricks designed and prepared in this invention. It should be noted that in practical applications, when continuous de-icing is required, the energy storage de-icing block bricks need to be combined with measures such as low-power continuous heating, intermittent pulsed heating, and drainage optimization to achieve long-term anti-icing effects.

[0062] The above description is merely an embodiment of the present invention and is not intended to limit the present invention in any way. The present invention can also have other embodiments based on the above structure and function, which will not be listed hereafter. Therefore, any simple modifications, equivalent changes, and alterations made by those skilled in the art to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A type of energy storage and de-icing block brick based on industrial waste, characterized in that, The device includes a hollow brick body (1), a brick cover (2) disposed on the top of the hollow brick body (1), and a capacitor array disposed in the cavity of the hollow brick body (1). The hollow brick body (1) is a rectangular hollow structure with an open top. The brick cover (2) is a rectangular cover plate that is adapted to the hollow brick body (1) and is bonded and fixed between the two. The capacitor array includes multiple capacitor cells (3) connected in series. A separator (4) is disposed between each two adjacent capacitor cells (3). The capacitor cell (3) includes an anode electrode (5), an anode electrolyte (6), a separator (7), a cathode electrolyte (8), and a cathode electrode (9) connected in sequence. Titanium metal wires (10) are led out from the anode electrode (5) and the cathode electrode (9) as connecting parts. The gap between the hollow brick body (1) and the capacitor cell (3) is filled with light-cured resin and encapsulated.

2. The energy storage and de-icing block brick based on industrial waste as described in claim 1, characterized in that, The outer length, width and height of the hollow brick body (1) are 240mm, 115mm and 40mm respectively, and the length, width and height of its cavity are 137mm, 23mm and 25mm respectively. The length, width and height of the brick cover (2) are 240mm, 115mm and 13mm respectively. After the hollow brick body (1) and the brick cover (2) are assembled, the length, width and height of the whole brick are 240mm, 115mm and 53mm respectively.

3. The energy storage and de-icing block brick based on industrial waste as described in claim 1 or 2, characterized in that, The capacitor array inside the hollow brick body (1) includes 5 capacitor cells (3) connected in series. The overall length, width and height of each capacitor cell (3) are 25mm, 23mm and 25mm respectively.

4. The energy storage and de-icing block brick based on industrial waste as described in claim 3, characterized in that, Both the separator (4) and the separator (7) are made of polypropylene membrane with a thickness of 3 mm.

5. The energy storage and de-icing block brick based on industrial waste as described in claim 1, characterized in that, The anode electrode (5) and the cathode electrode (9) are made of the same material and have the same structure, and are collectively referred to as electrode A. The preparation method of electrode A includes: (1) Sodium hydroxide solution and sodium silicate solution are mixed at a mass ratio of 2:15 to obtain mixture A; the concentration of sodium hydroxide solution is 320 g / L, and the mass fraction of SiO2 in sodium silicate solution is 8.0% and the mass fraction of Na2O is 26.8%; (2) Mix the mixture A obtained in step (1) with fly ash at a mass ratio of 1:2, and stir the mixture at high speed until it is uniformly mixed to obtain mixture B; (3) Pour the mixture B into the electrode mold and shake for 2-5 minutes to remove air bubbles. The center of the top end face of the electrode mold has an opening for inserting a titanium wire (10). After removing the air bubbles, insert a titanium wire (10) vertically into the mold from the opening on the top end face of the electrode mold as the connection part of the electrode. The titanium wire (10) extends 70-100 mm out of the top of the electrode mold. Then cure at 60°C for 72 hours. After demolding, the electrode blank is obtained. (4) Polish the electrode blank obtained in step (3) with sandpaper, wash it several times with distilled water to remove surface dust, and then dry it at 160℃ for 1-2 hours to obtain the electrode sample. (5) Place the electrode sample into a high-pressure reactor, add 3,4-ethylenedioxythiophene and hydrochloric acid, seal the high-pressure reactor and place it in an oven at 155°C for 15-20 h; after completion, wash the obtained product with methanol 3-5 times and then dry it at room temperature to obtain electrode A.

6. The energy storage and de-icing block brick based on industrial waste as described in claim 5, characterized in that, In step (3), the inner cavity of the electrode mold has a length, width, and height of 25mm, 5mm, and 25mm, respectively, and the top of the electrode mold has a size of 25mm×5mm. After demolding, an electrode blank with a length, width, and height of 25mm, 5mm, and 25mm is obtained. In step (5), the concentration of 3,4-ethylenedioxythiophene is 0.85M and the volume used is 800μL. The concentration of hydrochloric acid is 12M and the volume used is 1600μL.

7. The energy storage and de-icing block brick based on industrial waste as described in claim 1, characterized in that, The anolyte (6) and the cathode electrolyte (8) are made of the same material and have the same structure. They are both gel electrolytes, which are prepared according to the following method: Polyvinyl alcohol was dissolved in 1M H2SO4 solution at 80°C with stirring. The mass ratio of polyvinyl alcohol to H2SO4 solution was 3g:20mL. The mixture was stirred for 1 hour to obtain a mixed solution. The mixed solution was poured into a mold with an inner cavity length, width, and height of 25mm, 5mm, and 25mm, respectively. The mold and the mixed solution inside the mold were placed in an environment of -20°C for 30 minutes, and then removed and placed at room temperature for 30 minutes. This was repeated as one cycle. Three cycles were repeated in this manner, with each cycle lasting 1 hour. After demolding, a gel electrolyte with a length, width, and height of 25mm, 5mm, and 25mm was obtained.

8. The energy storage and de-icing block brick based on industrial waste as described in claim 1, characterized in that, The preparation methods of the hollow brick body (1) and the brick cover (2) include: (1) Sodium hydroxide solution and sodium silicate solution are mixed at a mass ratio of 2:15 to obtain mixture A; the concentration of sodium hydroxide solution is 320 g / L, and the mass fraction of SiO2 in sodium silicate solution is 8.0% and the mass fraction of Na2O is 26.8%; (2) Mix the mixture A obtained in step (1) with fly ash at a mass ratio of 1:2, and stir the mixture at high speed until it is uniformly mixed to obtain mixture B; (3) Pour the mixture B into the cavity brick body (1) mold and the brick cover (2) mold respectively, shake for 2-5 minutes to remove air bubbles, and then cure the cavity brick body (1) mold and the mixture B inside it, and the brick cover (2) mold and the mixture B inside it at 60°C for 72-80 hours. After demolding, the cavity brick body (1) and the brick cover (2) are obtained.

9. The energy storage and de-icing block brick based on industrial waste as described in claim 1, characterized in that, The assembly method includes: placing the assembled capacitor cell (3) into the cavity of the hollow brick (1), placing 5 capacitor cells (3) side by side in the cavity of each hollow brick (1) to form a capacitor array, and placing a polypropylene diaphragm as a separation diaphragm (4) between two adjacent capacitor cells (3); connecting the titanium wires (10) between two adjacent capacitor cells (3) with wires (11), wherein the titanium wire (10) on the anode electrode (5) of the previous capacitor cell (3) is connected to the titanium wire on the cathode electrode (9) of the adjacent capacitor cell (3). (10) Connect, the capacitor cells (3) at both ends leave titanium wires (10) on the cathode electrode (9) and titanium wires (10) on the anode electrode (5) respectively. The two titanium wires (10) are bent out from the top of the cavity brick (1) for further connection of solar integrated circuits. The gap between the cavity brick (1) and the capacitor cells (3) is filled with light-curing resin. The brick cover (2) is placed on the top of the cavity brick (1). The brick cover (2) and the cavity brick (1) are fixed with epoxy resin to complete the encapsulation and obtain the energy storage de-icing block brick.

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