Acid-activated regenerative brick-concrete micro-powder-partially-geopolymers battery and preparation method thereof

Abstract

The application discloses an acid-activated regenerated brick-mixed micro-powder-metakaolin geopolymer battery and a preparation method thereof. The geopolymer battery is formed by sequentially stacking and pouring a geopolymer positive electrode layer, a geopolymer electrolyte layer and a geopolymer negative electrode layer. The three layers all comprise regenerated brick-mixed micro-powder and metakaolin. The preparation method comprises the following steps: preparing geopolymer positive electrode layer slurry, geopolymer electrolyte layer slurry and geopolymer negative electrode layer slurry respectively; sequentially pouring the positive electrode layer, the electrolyte layer and the negative electrode layer, and vibrating and standing each layer after pouring according to preset parameters, and arranging copper-plated steel fibers in the whole structure by a magnetic field; and curing and coating the whole structure. The geopolymer battery has excellent conductivity, load capacity and interlayer bonding strength, and the whole structure is stable.

Description

Technical Field

[0001] This invention belongs to the field of road engineering materials and electrochemical energy storage technology, specifically relating to an acid-activated regenerated brick-mixed micro-powder-metakaolin geological polymer battery and its preparation method. Background Technology

[0002] Traditional dry cell batteries (such as zinc-manganese batteries and alkaline batteries) have long suffered from two major problems: First, the traditional dry cell battery structure uses a metal casing (zinc canister) to encapsulate the electrolyte, which also serves as the negative electrode. After the battery is depleted, a large amount of zinc remains (approximately 60-70% unreacted), resulting in low metal utilization and resource waste. Second, heavy metals such as zinc, manganese, and mercury in discarded batteries can easily leach into soil and water bodies through corrosion of the casing, thereby polluting the entire ecosystem and posing a lasting threat to the environment. These technical problems are becoming increasingly prominent and urgently require solutions through technological innovation.

[0003] In recent years, with the accelerating pace of urbanization, old city renovation, and urban village redevelopment, the amount of construction waste generated has increased significantly. Construction waste is generally divided into low-brick-concrete content concrete waste and high-brick-concrete content brick-concrete waste. After processing, these two types of construction waste can be used to obtain recycled concrete aggregate and recycled brick-concrete aggregate, respectively. If further finely ground, recycled concrete powder and recycled brick-concrete powder can be obtained accordingly. Recycled concrete aggregate / powder comes from waste concrete, while recycled brick-concrete aggregate / powder comes from waste bricks and tiles. Concrete and bricks and tiles (i.e., red bricks, red brick fragments, tile pieces, etc.) are two different solid waste materials.

[0004] With the increasing efforts in urban and rural town renovation, many village and town buildings have been demolished, especially brick-concrete structures. The resulting brick-concrete construction waste is substantial and requires appropriate solid waste treatment methods to transform it into usable recycled brick-concrete powder. This powder can then be explored as a functional matrix material for the preparation of geopolymer batteries. The recycled brick-concrete powder has a high content of alumina and silica, exhibiting certain pozzolanic activity, and can be used as a precursor material to prepare geopolymer cementitious materials through activation.

[0005] In recent years, geopolymer batteries have attracted much attention due to their green and environmentally friendly characteristics. However, their further development still faces many technical bottlenecks: First, the electrolyte stability is insufficient. Existing geopolymer electrolytes mainly rely on aqueous solutions in the pores to conduct ions, which is easily affected by water evaporation or leakage, leading to a decrease in ionic conductivity and overall performance degradation. Second, the conductivity is poor. The high interfacial resistance between the electrode and the electrolyte limits the charge transfer efficiency, resulting in low battery discharge efficiency. Third, the interlayer contact impedance is high. Existing battery structures are mostly simple stacking with weak interlayer bonding and a lack of directional conductive network, resulting in high contact resistance and excessive overall internal resistance, which seriously restricts the overall electrochemical performance of the battery. Fourth, the structure is easily separable. The functional layers rely only on physical contact and lack effective chemical bonding or mechanical interlocking. Under cyclic use or stress, delamination and peeling are prone to occur, causing structural failure. Therefore, there is an urgent need to develop an acid-activated regenerated brick-mixed micropowder-metakaolin geopolymer battery and its preparation method to promote the further development of this technology.

[0006] The invention patent with publication number CN112652782A discloses an environmentally friendly geopolymer battery and its preparation method. The geopolymer powder includes blast furnace slag and fly ash, and a geopolymer slurry is prepared by alkali activation. However, the blast furnace slag and fly ash used in this technical solution are industrial solid wastes, and their chemical composition differs from construction waste, thus failing to achieve resource utilization of construction waste. Furthermore, the alkali activation process damages the mechanical properties of the geopolymer, affecting the structural strength and stability of the geopolymer battery and limiting its electron transport capability. The preparation process does not consider the casting sequence and interface treatment of each functional layer, resulting in poor interlayer adhesion and easy delamination, affecting the overall structural stability and electrochemical performance of the battery. Summary of the Invention

[0007] To address the problems existing in the prior art, this invention provides an acid-activated regenerated brick-concrete micropowder-metakaolin geopolymer battery. The geopolymer battery is formed by sequentially stacking and casting a geopolymer positive electrode layer, a geopolymer electrolyte layer, and a geopolymer negative electrode layer, and is integrally cured and molded. The raw materials for preparing the geopolymer positive electrode layer, the geopolymer electrolyte layer, and the geopolymer negative electrode layer all include regenerated brick-concrete micropowder and metakaolin, and the geopolymer slurry is prepared by acid activation.

[0008] Preferably, the mass percentage of each substance in the geopolymer positive electrode layer is as follows: 37-46 wt% recycled brick-mixed micro powder, 7-10 wt% metakaolin, 25-35 wt% conductive material, 12-18 wt% composite acid, and 4-8 wt% deionized water, with the sum of the contents of each substance being 100 wt%.

[0009] In any of the above embodiments, it is preferred that, in the geopolymer positive electrode layer: the recycled brick-concrete micro powder is a product obtained by processing construction waste generated from the demolition of brick-concrete buildings, and its brick-concrete content is not less than 90%; the chemical composition of the recycled brick-concrete micro powder has a total mass of 80-90 wt% alumina and silicon dioxide, a total mass of 4-6 wt% sodium oxide and potassium oxide, a mass ratio of alumina to silicon dioxide of 1:1.2-1.5, and a mass ratio of sodium oxide to potassium oxide of 1:1.

[0010] The recycled brick-mixed powder includes two particle sizes: 0.075mm ≤ particle size ≤ 0.5mm and 0mm < particle size < 0.075mm. The two particle sizes account for 20-30 wt% of the mass of the recycled brick-mixed powder, respectively, and 70-80 wt% of the particle size ≤ 0.075mm and particle size < 0.075mm.

[0011] The metakaolin contains 90-95 wt% alumina and silica, with a mass ratio of 1:1.2-1.5. The metakaolin comprises two particle sizes: 5 μm ≤ 10 μm and 1 μm ≤ < 5 μm. The percentage of each particle size range in the metakaolin is 20-30 wt% for 5 μm ≤ 10 μm and 70-80 wt% for 1 μm ≤ < 5 μm.

[0012] The conductive material comprises, by mass percentage, 85-92 wt% electrolytic manganese dioxide, 5-12 wt% conductive carbon black, and 1-5 wt% conductive fiber; the conductive fiber is composed of chopped carbon fiber, copper-plated steel fiber, and graphite whiskers, with a mass ratio of 1.8-2.2:2.8-3.5:1 for the chopped carbon fiber, copper-plated steel fiber, and graphite whiskers.

[0013] The electrolytic manganese dioxide has a particle size of no more than 75 μm; the conductive carbon black has a particle size controlled within the range of 10-20 nm; the short-cut carbon fibers have a diameter controlled within the range of 5-8 μm and a length controlled within the range of 3-5 mm; the copper-plated steel fibers have a diameter controlled within the range of 0.1-0.2 mm and a length controlled within the range of 3-5 mm, and the copper layer thickness controlled within the range of 1-3 μm; the graphite whiskers have a diameter controlled within the range of 0.5-1 μm and a length controlled within the range of 0.8-1.5 mm.

[0014] The composite acid is composed of sulfuric acid and phosphoric acid, with the mass ratio of sulfuric acid to phosphoric acid being 1:6-8; the concentration of sulfuric acid is 60%, and the concentration of phosphoric acid is 85%.

[0015] In any of the above embodiments, it is preferred that the mass percentage of each substance in the geopolymer electrolyte layer is as follows: 40-44 wt% recycled brick-mixed powder, 10-12 wt% metakaolin, 2-2.5 wt% foaming agent, 1.5-2.2 wt% foaming stabilizer, 2.2-3 wt% basalt fiber, 28-33 wt% composite acid, and 8-10 wt% deionized water, with the sum of the contents of each substance being 100 wt%.

[0016] In any of the above embodiments, it is preferred that, in the geopolymer electrolyte layer: the recycled brick-concrete micro powder is a product obtained by processing construction waste generated from the demolition of brick-concrete buildings, and its brick-concrete content is not less than 90%; the chemical composition of the recycled brick-concrete micro powder has a total mass of 80-90 wt% alumina and silicon dioxide, a total mass of 4-6 wt% sodium oxide and potassium oxide, a mass ratio of alumina to silicon dioxide of 1:1.2-1.5, and a mass ratio of sodium oxide to potassium oxide of 1:1.

[0017] The recycled brick-mixed powder includes two particle sizes: 0.075mm ≤ particle size ≤ 0.5mm and 0mm < particle size < 0.075mm. The two particle sizes account for 20-30 wt% of the mass of the recycled brick-mixed powder, respectively, and 70-80 wt% of the particle size ≤ 0.075mm and particle size < 0.075mm.

[0018] The metakaolin contains 90-95 wt% alumina and silica, with a mass ratio of 1:1.2-1.5. The metakaolin comprises two particle sizes: 5 μm ≤ 10 μm and 1 μm ≤ < 5 μm. The percentage of each particle size range in the metakaolin is 20-30 wt% for 5 μm ≤ 10 μm and 70-80 wt% for 1 μm ≤ < 5 μm.

[0019] The foaming agent is composed of hydrogen peroxide and potassium permanganate, and the mass ratio of hydrogen peroxide to potassium permanganate is 1:1.5-2; the foaming stabilizer is calcium stearate; the diameter of the basalt fiber is controlled within the range of 15-25 μm and the length is controlled within the range of 3-6 mm.

[0020] The composite acid is composed of sulfuric acid and phosphoric acid, with the mass ratio of sulfuric acid to phosphoric acid being 1:6-8; the concentration of sulfuric acid is 60%, and the concentration of phosphoric acid is 85%.

[0021] In any of the above schemes, it is preferred that the mass percentage of each substance in the geopolymer negative electrode layer is as follows: 38-46 wt% recycled brick-mixed micro powder, 6-10 wt% metakaolin, 12-18 wt% zinc stearate-coated aluminum powder, 10-20 wt% conductive material, 12-18 wt% composite acid, and 4-6 wt% deionized water, with the sum of the contents of each substance being 100 wt%.

[0022] In any of the above embodiments, it is preferred that, in the geopolymer negative electrode layer: the recycled brick-concrete micro powder is a product obtained by processing construction waste generated from the demolition of brick-concrete buildings, and its brick-concrete content is not less than 90%; the chemical composition of the recycled brick-concrete micro powder has a total mass of 80-90 wt% alumina and silicon dioxide, a total mass of 4-6 wt% sodium oxide and potassium oxide, a mass ratio of alumina to silicon dioxide of 1:1.2-1.5, and a mass ratio of sodium oxide to potassium oxide of 1:1.

[0023] The recycled brick-mixed powder includes two particle sizes: 0.075mm ≤ particle size ≤ 0.5mm and 0mm < particle size < 0.075mm. The two particle sizes account for 20-30 wt% of the mass of the recycled brick-mixed powder, respectively, and 70-80 wt% of the particle size ≤ 0.075mm and particle size < 0.075mm.

[0024] The metakaolin contains 90-95 wt% alumina and silica, with a mass ratio of 1:1.2-1.5. The metakaolin comprises two particle sizes: 5 μm ≤ 10 μm and 1 μm ≤ < 5 μm. The percentage of each particle size range in the metakaolin is 20-30 wt% for 5 μm ≤ 10 μm and 70-80 wt% for 1 μm ≤ < 5 μm.

[0025] The particle size of the zinc stearate-coated aluminum powder is no greater than 10 μm, the thickness of the zinc stearate layer is no greater than 1 μm, and the particle size of the aluminum powder is controlled within the range of 100-200 nm.

[0026] The conductive material comprises, by mass percentage, 85-92 wt% electrolytic manganese dioxide, 5-12 wt% conductive carbon black, and 1-5 wt% conductive fiber; the conductive fiber is composed of chopped carbon fiber, copper-plated steel fiber, and graphite whiskers, with a mass ratio of 1.8-2.2:2.8-3.5:1 for the chopped carbon fiber, copper-plated steel fiber, and graphite whiskers.

[0027] The electrolytic manganese dioxide has a particle size of no more than 75 μm; the conductive carbon black has a particle size controlled within the range of 10-20 nm; the short-cut carbon fibers have a diameter controlled within the range of 5-8 μm and a length controlled within the range of 3-5 mm; the copper-plated steel fibers have a diameter controlled within the range of 0.1-0.2 mm and a length controlled within the range of 3-5 mm, and the copper layer thickness controlled within the range of 1-3 μm; the graphite whiskers have a diameter controlled within the range of 0.5-1 μm and a length controlled within the range of 0.8-1.5 mm.

[0028] The composite acid is composed of sulfuric acid and phosphoric acid, with the mass ratio of sulfuric acid to phosphoric acid being 1:6-8; the concentration of sulfuric acid is 60%, and the concentration of phosphoric acid is 85%.

[0029] This invention also provides a method for preparing an acid-activated regenerated brick-mixed micropowder-metakaolin geopolymer battery, the preparation method comprising the following steps in sequence: Step 1: Prepare geopolymer positive electrode slurry, geopolymer electrolyte slurry, and geopolymer negative electrode slurry according to the designed material ratio, and set them aside after preparation; Step 2: Fix the electromagnetic coil horizontally on the electric vibration table, and then place the molding mold horizontally inside the working area of ​​the electromagnetic coil; according to the designed height ratio of the geopolymer positive electrode layer, geopolymer electrolyte layer and geopolymer negative electrode layer, pour the geopolymer positive electrode layer slurry into the molding mold, and then vibrate and let it stand in sequence to form the geopolymer positive electrode layer. Step 3: According to the designed height ratio of the geopolymer positive electrode layer, geopolymer electrolyte layer and geopolymer negative electrode layer, pour the geopolymer electrolyte layer slurry onto the geopolymer positive electrode layer in the molding mold, and then vibrate and let it stand in sequence to form the geopolymer electrolyte layer. Step 4: According to the designed height ratio of the geopolymer positive electrode layer, geopolymer electrolyte layer and geopolymer negative electrode layer, pour the geopolymer negative electrode layer slurry onto the top of the geopolymer electrolyte layer in the molding mold, and then vibrate it to form the geopolymer negative electrode layer. Step 5: The electric vibration table continues to vibrate, and the electromagnetic coil is turned on at the same time. Under the combined action of vibration and magnetic field, the copper-plated steel fibers in the overall structure composed of the geopolymer positive electrode layer, the geopolymer electrolyte layer and the geopolymer negative electrode layer gradually align laterally along the direction of magnetic induction lines. After the vibration reaches the preset time, the electric vibration table stops vibrating, and the electromagnetic coil continues to work, further enabling the copper-plated steel fibers to complete the directional alignment along the direction of magnetic induction lines. Step Six: Seal the molding mold and its internal structure with plastic film, and place it in a curing box for the first curing. After the first curing is completed, demold the mold, seal the entire structure with plastic film, and place it in the curing box again for the second curing. After the second curing is completed, remove the plastic film; attach conductive metal sheets to the sides of the geopolymer positive electrode layer and the geopolymer negative electrode layer respectively. Step 7: Apply a coating to the outer surface of the overall structure after removing the plastic film using a spray gun to obtain the acid-activated regenerated brick-concrete micro-powder-metakaolin geological polymer battery.

[0030] Preferably, in step one, the preparation of the geopolymer positive electrode slurry includes the following steps in sequence: Step 1.1: Place the recycled brick-mixed micro powder and the kaolin of each particle size into a drying oven for drying treatment. The drying temperature is 100-120℃ and the drying time is 6-8h. First, immerse the copper-plated steel fiber in 5% nitric acid for 10-20 minutes to remove the surface oxide layer; then immerse the copper-plated steel fiber in 2% hydroxypropyl methylcellulose pretreatment agent and stir for 30-60 minutes. After removal, rinse with distilled water to remove excess pretreatment agent from the surface; then place the copper-plated steel fiber in a drying oven for drying at 60-80℃ for 1.5-2.5 hours. Step 1.2: Sulfuric acid and phosphoric acid are slowly added dropwise to deionized water and mixed evenly at room temperature to obtain a composite acid activator; Step 1.3: Put the recycled brick-mixed micro powder of various particle sizes, the kaolin of various particle sizes, the short-cut carbon fiber, the copper-plated steel fiber, and the graphite whiskers into a mixer and stir them. The stirring temperature is room temperature, the stirring speed is 100-300 rpm, and the stirring time is 5-8 minutes. Step 1.4: Place the electrolytic manganese dioxide and conductive carbon black into a mixer and continue stirring. The stirring temperature is room temperature, the stirring speed is 100-300 rpm, and the stirring time is 2-3 minutes. Step 1.5: Place the composite acid activator into a mixer and continue stirring. The stirring temperature is room temperature, the stirring speed is 100-300 rpm, and the stirring time is 2-5 minutes.

[0031] In any of the above schemes, it is preferred that, in step one, the preparation of the geopolymer electrolyte layer slurry includes the following steps in sequence: Step 2.1: Place the recycled brick-mixed micro powder and the kaolin of each particle size into a drying oven for drying treatment. The drying temperature is 100-120℃ and the drying time is 6-8h. Step 2.2: Sulfuric acid and phosphoric acid are slowly added dropwise to deionized water and mixed evenly at room temperature to obtain a composite acid activator; Step 2.3: Put the recycled brick-mixed micro powder of various particle sizes, the kaolin of various particle sizes, and the basalt fiber into a mixer and mix them. The mixing temperature is room temperature, the mixing speed is 100-300 rpm, and the mixing time is 5-8 minutes. Step 2.4: Put the potassium permanganate and foaming stabilizer from the foaming agent components into the mixer and continue to stir. The stirring temperature is room temperature, the stirring speed is 100-300 rpm, and the stirring time is 2-4 min. Step 2.5: Add hydrogen peroxide and compound acid activator from the foaming agent components to a mixer and continue stirring. The stirring temperature is room temperature, the stirring speed is 100-300 rpm, and the stirring time is 3-5 minutes.

[0032] In any of the above schemes, it is preferred that, in step one, the preparation of the geopolymer negative electrode slurry includes the following steps in sequence: Step 3.1: Place the recycled brick-mixed micro powder and the kaolin of each particle size into a drying oven for drying treatment. The drying temperature is 100-120℃ and the drying time is 6-8h. First, immerse the copper-plated steel fiber in 5% nitric acid for 10-20 minutes to remove the surface oxide layer; then immerse the copper-plated steel fiber in 2% hydroxypropyl methylcellulose pretreatment agent and stir for 30-60 minutes. After removal, rinse with distilled water to remove excess pretreatment agent from the surface; then place the copper-plated steel fiber in a drying oven for drying at 60-80℃ for 1.5-2.5 hours. Step 3.2: Sulfuric acid and phosphoric acid are slowly added dropwise to deionized water and mixed evenly at room temperature to obtain a composite acid activator; Step 3.3: Put the recycled brick-mixed micro powder of various particle sizes, the metakaolin of various particle sizes, zinc stearate coated aluminum powder, short carbon fiber, copper-plated steel fiber, and graphite whiskers into a mixer and stir them. The stirring temperature is room temperature, the stirring speed is 100-300 rpm, and the stirring time is 5-8 minutes. Step 3.4: Place the electrolytic manganese dioxide and conductive carbon black into a mixer and continue stirring. The stirring temperature is room temperature, the stirring speed is 100-300 rpm, and the stirring time is 2-3 minutes. Step 3.5: Place the composite acid activator into a mixer and continue stirring. The stirring temperature is room temperature, the stirring speed is 100-300 rpm, and the stirring time is 2-5 minutes.

[0033] In any of the above schemes, it is preferred that, in steps two to four, the overall shape of the prepared geopolymer battery includes any one of cube, cuboid, and cylindrical shapes, and the height ratio of the geopolymer positive electrode layer, the geopolymer electrolyte layer, and the geopolymer negative electrode layer is 1:4.2-5:1.

[0034] In any of the above schemes, the preferred method is that, in step two, the vibration and settling process of the geopolymer positive electrode layer is as follows: First, the geopolymer positive electrode layer slurry is poured into the molding mold according to the designed height ratio. The electric vibration table is started, and preliminary compaction is performed at room temperature with a vibration frequency of 50-60Hz and a vibration time of 3-5min. Then, the electric vibration table is turned off, and the mixture is allowed to stand naturally at room temperature for 20-30min with an ambient relative humidity of 20-30%.

[0035] In any of the above schemes, the preferred method is that, in step three, the vibration and settling process of the geopolymer electrolyte layer is as follows: First, the geopolymer electrolyte layer slurry is poured into the mold above the geopolymer positive electrode layer according to the designed height ratio. The electric vibration table is started, and preliminary compaction is performed at room temperature. The vibration frequency is 1.5-1.8 times the vibration frequency of the geopolymer positive electrode layer, and the vibration time is 1.8-2 times the vibration time of the geopolymer positive electrode layer. Then, the electric vibration table is turned off, and the mixture is allowed to stand naturally at room temperature for 30-40 minutes with a relative humidity of 20-30%.

[0036] In any of the above schemes, the preferred method is that, in step four, the vibration process of the geopolymer negative electrode layer is as follows: the geopolymer negative electrode layer slurry is poured onto the top of the geopolymer electrolyte layer in the molding mold according to the designed height ratio, the electric vibration table is started, and preliminary compaction is performed at room temperature with a vibration frequency of 50-60Hz and a vibration time of 3-5min.

[0037] In any of the above schemes, it is preferred that, in step five, the process parameters for the directional arrangement of the copper-plated steel fibers are as follows: when vibration and magnetic field act together, the electromagnetic coil is a rectangular solenoid with an inner width of 20-30cm, a length of 90-100cm, and 500-600 turns. The electromagnetic coil operates under a 24V DC voltage with a working current of 3-4A, a magnetic field strength of not less than 30mT, a vibration frequency of 50-60Hz, and a duration of combined vibration and magnetic field action of 5-8min; when only the magnetic field acts, the duration of magnetic field action is 25-30min.

[0038] In any of the above schemes, it is preferred that in step six, two curing processes are carried out, with a curing temperature of 60-80℃ and an ambient relative humidity of not less than 95%. The first curing time is 72 hours and the second curing time is 96 hours.

[0039] In any of the above schemes, it is preferred that, in step seven, the coating material is a silane impregnating agent with a thickness of 0.5-0.8 mm and a spraying pressure of 0.3-0.6 MPa.

[0040] In this invention, the recycled brick-mixed powder includes two particle size ranges: 0.075mm ≤ particle size ≤ 0.5mm and 0mm < particle size < 0.075mm; the metakaolin includes two particle size ranges: 5μm ≤ particle size ≤ 10μm and 1μm ≤ particle size < 5μm. For each particle size range, the material is passed through two sieves sequentially, and the resulting particle size is between the upper and lower sieve openings. For example, 1μm ≤ particle size < 5μm means that the material is passed through a 5μm sieve and a 1μm sieve sequentially, and the resulting particle size is between 1 and 5μm.

[0041] The recycled brick-concrete micro-powder used in this invention is a product obtained by processing construction waste generated from the demolition of brick-concrete buildings. This processing includes a series of steps such as crushing, fine grinding, sorting, purification, and quality control, all completed uniformly in a factory. There are no special requirements for the processing parameters, as long as the particle size at each stage meets the requirements of this invention. Regarding the chemical composition of the recycled brick-concrete micro-powder, it is sufficient to ensure that the content of alumina, silicon dioxide, sodium oxide, and potassium oxide meets the requirements of this invention; there are no special requirements for other chemical components. Similarly, regarding the chemical composition of metakaolin, it is sufficient to ensure that the content of alumina and silicon dioxide meets the requirements of this invention; there are no special requirements for other chemical components.

[0042] The copper-plated steel fibers used in this invention are produced uniformly by the factory, and there are no special requirements for the production process and parameters, as long as the particle size, length, and copper layer thickness meet the requirements of this invention. Similarly, the zinc stearate-coated aluminum powder used in this invention is also produced uniformly by the factory, and there are no special requirements for the production process and parameters, as long as the particle size, zinc stearate layer thickness, and aluminum powder particle size meet the requirements of this invention.

[0043] In the geopolymer electrolyte layer, hydrogen peroxide decomposes to produce a porous structure, forming interconnected pores with a pore size of 10-50 μm. Potassium permanganate, in addition to acting as a catalyst for the decomposition reaction of hydrogen peroxide, also decomposes it to generate manganese dioxide. Some of the manganese dioxide diffuses to the positive electrode layer through liquid phase bridging and solidifies, anchoring itself to the positive electrode pore wall to form in-situ catalytic active sites. Calcium stearate acts as both a foaming stabilizer and a dendrite inhibitor, as well as a microcrack repair agent: (1) Foaming stabilization, forming uniform pores inside the geopolymer electrolyte region, which is beneficial to the migration of charges and solutions in the electrolyte; (2) Acid-triggered self-repair, when microcracks occur in the electrolyte region, a composite acid-activated solution will seep into the cracks, and the generated gypsum crystals can fill the cracks, restoring the mechanical strength of the geopolymer matrix in the electrolyte region.

[0044] This invention uses acid activation to prepare geopolymer slurry, which fundamentally avoids alkali-aggregate reaction. The resulting geopolymer has extremely low dielectric loss due to its extremely low content of free alkali metal ions. This characteristic helps to suppress electron transport in the battery, thereby improving battery efficiency. Traditional alkali activation does not have this advantage.

[0045] In this invention, a dual-function conductive network can be formed, with copper-plated steel fibers providing an electronic conduction path and short-cut carbon fibers enhancing interfacial charge transfer through stacking; in addition, the oriented copper-plated steel fibers can improve the mechanical strength of the geopolymer.

[0046] In the three-layer structure (positive electrode layer, electrolyte layer, and negative electrode layer) of the geopolymer battery of this invention, recycled brick-like micro-powder and metakaolin are used as the main precursor materials. Their use stems from their complementary chemical composition and microstructural characteristics, supporting efficient acid-induced polymerization reactions to form a stable network structure. Specifically: In terms of chemical composition, the recycled brick-concrete micro powder is rich in SiO2 and Al2O3, and also contains auxiliary components such as Fe2O3 and CaO. These aluminosilicates provide the main raw material framework for the geopolymerization reaction and promote the acid-activated Al2O3 polymerization. 3+ and Si 4+ Dissolution and condensation occur simultaneously. CaO in the recycled brick-concrete powder reacts with H₂SO₄ to form gypsum, filling micropores and inhibiting the leaching of heavy metal ions. Metakaolin provides a higher Al₂O₃ content, enhancing the Al source supply, optimizing the P / Al molar ratio, and achieving a more complete silica-alumina phosphate network polymerization.

[0047] In terms of microstructure, recycled brick-mixed powder, derived from waste bricks, contains an amorphous phase and consists of porous, irregular particles. This promotes the uniform distribution of the foaming agent, forming interconnected pores that facilitate ion conduction. Metakaolin, with its highly amorphous layered structure, rapidly recrystallizes its layered aluminosilicates under acid excitation, forming a dense, cross-linked cementitious network that enhances the uniformity and stability of the overall structure. The two components synergistically regulate the Al / Si molar ratio, avoiding the looseness of recycled brick-mixed powder alone or the excessive density of metakaolin alone, thus achieving optimal porosity and reduced microcracks.

[0048] In terms of electrical conductivity, the dense polymer network formed by recycled brick-mixed powder and metakaolin has low dielectric loss and improves ion conduction efficiency.

[0049] Regarding interlayer bonding, the irregular particles of recycled brick-concrete micropowder complement the layered structure of metakaolin, forming a microscopic interlocking interface and enhancing interlayer bonding strength. In layered casting, subsequent layers are poured before the preceding layers are fully cured, promoting chemical co-condensation, reducing interfacial voids, and improving ion transport and mechanical properties. Compared to single materials, synergistic formulation avoids interfacial separation caused by loose / overly dense materials, ensuring the integrity of the battery.

[0050] The positive and negative electrode layers of this invention use copper-plated steel fibers, which combine the high strength of steel with the excellent conductivity and corrosion resistance of copper, providing an electron conduction path. At the same time, the magnetic field is oriented to form a three-dimensional network, optimizing the conductivity and mechanical properties of the positive and negative electrode layers.

[0051] The negative electrode layer of this invention uses zinc stearate-coated aluminum powder. Zinc soap, acting as a dendrite / corrosion inhibitor, reacts with H₂SO₄ to form self-healing zinc soap, maintaining the negative electrode activity. The hydrophobic chains of zinc stearate form a dense barrier, inhibiting passivation and ensuring the reversible electrochemical reaction of the battery's negative electrode. Using zinc stearate-coated aluminum powder also reduces contact resistance fluctuations and slows dendrite growth; the generated zinc soap can dynamically repair microcracks.

[0052] In this invention, the material selection and proportioning, casting sequence, and process parameters of the geopolymer positive electrode layer, geopolymer electrolyte layer, and geopolymer negative electrode layer are crucial, especially the vibration and settling parameters of each layer, which directly affect the interlayer bonding ability. These parameters can regulate the polymerization reaction rate, pore distribution, and interfacial compatibility to ensure optimized battery performance. Vibration and settling parameters, in particular, directly affect the interlayer bonding ability. Casting in layers sequentially within the same mold allows control over the hydration level of each layer. Casting the next layer before the previous layer is fully hydrated ensures the connection between layers, maintains the overall integrity of the battery, strengthens the interlayer bonding ability, and thus improves ion transport capacity and mechanical properties.

[0053] The acid-activated regenerated brick-mixed micropowder-metakaolin geopolymer battery and its preparation method of the present invention have the following beneficial effects: (1) The geopolymer electrolyte of the present invention has good stability. By constructing a self-locking hydrogel network / solid electrolyte skeleton, the structural stability and water retention capacity of the geopolymer electrolyte are significantly improved, and the ionic conductivity decay caused by water evaporation or leakage is effectively suppressed, thereby ensuring that the battery can maintain excellent performance stability and reliability under long-term cycling and complex environments.

[0054] (2) The geopolymer battery of the present invention has excellent interlayer bonding strength. By adopting a molding method of sequential casting and integrated curing, and by precisely controlling the time window of interlayer casting, a strong bond between layers is achieved. This bonding method is far superior to physical stacking, effectively preventing delamination and ensuring that the geopolymer battery maintains its structural integrity under long-term use and external stress.

[0055] (3) The present invention constructs a three-dimensional oriented conductive fiber network by inducing magnetic field, forming a continuous electron / ion co-transmission channel between layers, which not only strengthens the interlayer bonding force, but also constructs a low-impedance internal conductive skeleton, significantly reducing the overall internal resistance of the battery.

[0056] (4) The geopolymer battery of the present invention has excellent conductivity and mechanical strength. By optimizing the materials and proportions of each layer, and combining sequential casting, integrated curing and molding, and magnetic field orientation method, the conductivity and load-bearing capacity of the geopolymer battery are significantly improved, and a balance between conductivity and load-bearing capacity is achieved.

[0057] (5) The preparation process of the geopolymer battery of the present invention is simple. It can be prepared by mixing and pouring the slurry of each layer according to the casting process of the present invention. No complicated assembly process is required, which is suitable for large-scale production. (6) The geopolymer battery of the present invention has great potential for low carbon and environmental protection, low cost and integrated structure and function. It has shown broad application prospects in the fields of green energy storage and infrastructure energy storage. At the same time, it provides a new way for the resource utilization of construction waste and effectively reduces carbon emissions in the construction field. Attached Figure Description

[0058] Figure 1 This is a photograph of the recycled brick-mixed micropowder in a preferred embodiment of the acid-activated recycled brick-mixed micropowder-metakaolin geopolymer battery and its preparation method according to the present invention. Figure 2 for Figure 1 A photograph of metakaolin in the illustrated embodiment; Figure 3 for Figure 1 A photograph of the copper-plated steel fiber in the illustrated embodiment; Figure 4 for Figure 1 A photograph of the zinc stearate-coated aluminum powder in the illustrated embodiment; Figure 5 for Figure 1 A physical image of the geopolymer electrolyte layer slurry prepared in the illustrated embodiment; Figure 6 for Figure 1 A physical image of the overall structure formed by the three layers of slurry after the copper-plated steel fibers are oriented and arranged in the embodiment shown. Figure 7for Figure 1 A physical diagram of the overall structure consisting of three layers of slurry after the second curing in the embodiment shown; Figure 8 for Figure 1 Microscopic morphology of the geopolymer electrolyte layer in the illustrated embodiment. Detailed Implementation

[0059] To further understand the invention, the following detailed description of the invention will be provided in conjunction with specific embodiments.

[0060] Example 1: According to a preferred embodiment of the acid-activated regenerated brick-concrete micropowder-metakaolin geopolymer battery of the present invention, the geopolymer battery is formed by sequentially stacking and casting a geopolymer positive electrode layer, a geopolymer electrolyte layer and a geopolymer negative electrode layer, and is integrally cured and molded; the raw materials for preparing the geopolymer positive electrode layer, the geopolymer electrolyte layer and the geopolymer negative electrode layer all include regenerated brick-concrete micropowder and metakaolin, and the geopolymer slurry is prepared by acid activation.

[0061] The mass percentage of each substance in the geopolymer positive electrode layer is as follows: 41 wt% recycled brick-mixed micro powder, 8 wt% metakaolin, 30 wt% conductive material, 15 wt% composite acid, and 6 wt% deionized water.

[0062] In the geopolymer cathode layer: The recycled brick-concrete micro powder is a product obtained by processing construction waste generated from the demolition of brick-concrete buildings, with a brick-concrete content of not less than 90%. The chemical composition of the recycled brick-concrete micro powder includes 85 wt% alumina and 5 wt% silicon dioxide, with a mass ratio of 1:1.3 for alumina and 1:1 for potassium oxide. The recycled brick-concrete micro powder comprises two particle size ranges, with the following percentages by mass: 25 wt% for particles 0.075 mm ≤ 0.5 mm and 75 wt% for particles 0 mm < 0.075 mm < 0.075 mm.

[0063] The metakaolin contains a total of 92 wt% alumina and silica, with a mass ratio of 1:1.3. The metakaolin comprises two particle sizes, with the particle sizes accounting for 25 wt% of the total mass of the metakaolin at a ratio of 5 μm ≤ particle size ≤ 10 μm and 75 wt% at a ratio of 1 μm ≤ particle size < 5 μm.

[0064] The conductive material comprises, by mass percentage, 88 wt% electrolytic manganese dioxide, 9 wt% conductive carbon black, and 3 wt% conductive fiber; the conductive fiber is composed of chopped carbon fiber, copper-plated steel fiber, and graphite whiskers, with a mass ratio of 2:3.2:1.

[0065] The electrolytic manganese dioxide has a particle size of no more than 75 μm; the conductive carbon black has a particle size controlled within the range of 10-20 nm; the short-cut carbon fibers have a diameter controlled within the range of 5-8 μm and a length controlled within the range of 3-5 mm; the copper-plated steel fibers have a diameter controlled within the range of 0.1-0.2 mm and a length controlled within the range of 3-5 mm, and the copper layer thickness controlled within the range of 1-3 μm; the graphite whiskers have a diameter controlled within the range of 0.5-1 μm and a length controlled within the range of 0.8-1.5 mm.

[0066] The composite acid is composed of sulfuric acid and phosphoric acid, with a mass ratio of sulfuric acid to phosphoric acid of 1:7; the concentration of sulfuric acid is 60%, and the concentration of phosphoric acid is 85%.

[0067] The mass percentages of each substance in the geopolymer electrolyte layer are as follows: 42.4 wt% recycled brick-mixed micro powder, 11 wt% metakaolin, 2.2 wt% foaming agent, 1.8 wt% foaming stabilizer, 2.6 wt% basalt fiber, 31 wt% composite acid, and 9 wt% deionized water.

[0068] In the geological polymer electrolyte layer: The recycled brick-concrete micro powder is a product obtained by processing construction waste generated from the demolition of brick-concrete buildings, with a brick-concrete content of not less than 90%. The chemical composition of the recycled brick-concrete micro powder includes 85 wt% alumina and 5 wt% silicon dioxide, with a mass ratio of 1:1.3 for alumina and 1:1 for potassium oxide. The recycled brick-concrete micro powder comprises two particle size ranges, with the following percentages by mass: 25 wt% for particles 0.075 mm ≤ 0.5 mm and 75 wt% for particles 0 mm < 0.075 mm < 0.075 mm.

[0069] The metakaolin contains a total of 92 wt% alumina and silica, with a mass ratio of 1:1.3. The metakaolin comprises two particle sizes, with the particle sizes accounting for 25 wt% of the total mass of the metakaolin at a ratio of 5 μm ≤ particle size ≤ 10 μm and 75 wt% at a ratio of 1 μm ≤ particle size < 5 μm.

[0070] The foaming agent is composed of hydrogen peroxide and potassium permanganate, with a mass ratio of hydrogen peroxide to potassium permanganate of 1:1.8; the foaming stabilizer is calcium stearate; the diameter of the basalt fiber is controlled within the range of 15-25 μm and the length is controlled within the range of 3-6 mm.

[0071] The composite acid is composed of sulfuric acid and phosphoric acid, with a mass ratio of sulfuric acid to phosphoric acid of 1:7; the concentration of sulfuric acid is 60%, and the concentration of phosphoric acid is 85%.

[0072] The mass percentage of each substance in the geopolymer negative electrode layer is as follows: 42 wt% recycled brick-mixed micro powder, 8 wt% metakaolin, 15 wt% zinc stearate-coated aluminum powder, 15 wt% conductive material, 15 wt% composite acid, and 5 wt% deionized water.

[0073] In the geopolymer negative electrode layer: The recycled brick-concrete micro powder is a product obtained by processing construction waste generated from the demolition of brick-concrete buildings, with a brick-concrete content of not less than 90%. The chemical composition of the recycled brick-concrete micro powder includes 85 wt% alumina and 5 wt% silicon dioxide, with a mass ratio of 1:1.3 for alumina and 1:1 for potassium oxide. The recycled brick-concrete micro powder comprises two particle size ranges, with the following percentages by mass: 25 wt% for particles 0.075 mm ≤ 0.5 mm and 75 wt% for particles 0 mm < 0.075 mm < 0.075 mm.

[0074] The metakaolin contains a total of 92 wt% alumina and silica, with a mass ratio of 1:1.3. The metakaolin comprises two particle sizes, with the particle sizes accounting for 25 wt% of the total mass of the metakaolin at a ratio of 5 μm ≤ particle size ≤ 10 μm and 75 wt% at a ratio of 1 μm ≤ particle size < 5 μm.

[0075] The particle size of the zinc stearate-coated aluminum powder is no greater than 10 μm, the thickness of the zinc stearate layer is no greater than 1 μm, and the particle size of the aluminum powder is controlled within the range of 100-200 nm.

[0076] The conductive material comprises, by mass percentage, 88 wt% electrolytic manganese dioxide, 9 wt% conductive carbon black, and 3 wt% conductive fiber; the conductive fiber is composed of chopped carbon fiber, copper-plated steel fiber, and graphite whiskers, with a mass ratio of 2:3.2:1.

[0077] The electrolytic manganese dioxide has a particle size of no more than 75 μm; the conductive carbon black has a particle size controlled within the range of 10-20 nm; the short-cut carbon fibers have a diameter controlled within the range of 5-8 μm and a length controlled within the range of 3-5 mm; the copper-plated steel fibers have a diameter controlled within the range of 0.1-0.2 mm and a length controlled within the range of 3-5 mm, and the copper layer thickness controlled within the range of 1-3 μm; the graphite whiskers have a diameter controlled within the range of 0.5-1 μm and a length controlled within the range of 0.8-1.5 mm.

[0078] The composite acid is composed of sulfuric acid and phosphoric acid, with a mass ratio of sulfuric acid to phosphoric acid of 1:7; the concentration of sulfuric acid is 60%, and the concentration of phosphoric acid is 85%.

[0079] This embodiment also provides a method for preparing an acid-activated regenerated brick-concrete micropowder-metakaolin geological polymer battery, the preparation method comprising the following steps in sequence: Step 1: Prepare geopolymer positive electrode slurry, geopolymer electrolyte slurry, and geopolymer negative electrode slurry according to the designed material ratio, and set them aside after preparation; Step 2: Fix the electromagnetic coil horizontally on the electric vibration table, and then place the molding mold horizontally inside the working area of ​​the electromagnetic coil; according to the designed height ratio of the geopolymer positive electrode layer, geopolymer electrolyte layer and geopolymer negative electrode layer, pour the geopolymer positive electrode layer slurry into the molding mold, and then vibrate and let it stand in sequence to form the geopolymer positive electrode layer. Step 3: According to the designed height ratio of the geopolymer positive electrode layer, geopolymer electrolyte layer and geopolymer negative electrode layer, pour the geopolymer electrolyte layer slurry onto the geopolymer positive electrode layer in the molding mold, and then vibrate and let it stand in sequence to form the geopolymer electrolyte layer. Step 4: According to the designed height ratio of the geopolymer positive electrode layer, geopolymer electrolyte layer and geopolymer negative electrode layer, pour the geopolymer negative electrode layer slurry onto the top of the geopolymer electrolyte layer in the molding mold, and then vibrate it to form the geopolymer negative electrode layer. Step 5: The electric vibration table continues to vibrate, and the electromagnetic coil is turned on at the same time. Under the combined action of vibration and magnetic field, the copper-plated steel fibers in the overall structure composed of the geopolymer positive electrode layer, the geopolymer electrolyte layer and the geopolymer negative electrode layer gradually align laterally along the direction of magnetic induction lines. After the vibration reaches the preset time, the electric vibration table stops vibrating, and the electromagnetic coil continues to work, further enabling the copper-plated steel fibers to complete the directional alignment along the direction of magnetic induction lines. Step Six: Seal the molding mold and its internal structure with plastic film, and place it in a curing box for the first curing. After the first curing is completed, demold the mold, seal the entire structure with plastic film, and place it in the curing box again for the second curing. After the second curing is completed, remove the plastic film; attach conductive metal sheets to the sides of the geopolymer positive electrode layer and the geopolymer negative electrode layer respectively. Step 7: Apply a coating to the outer surface of the overall structure after removing the plastic film using a spray gun to obtain the acid-activated regenerated brick-concrete micro-powder-metakaolin geological polymer battery.

[0080] In step one, the preparation of the geopolymer positive electrode slurry includes the following steps in sequence: Step 1.1: Place the recycled brick-mixed micro powder and the metakaolin of each particle size into a drying oven for drying treatment. The drying temperature is 110℃ and the drying time is 7h. First, the copper-plated steel fiber is immersed in 5% nitric acid for 15 minutes to remove the surface oxide layer; then, the copper-plated steel fiber is immersed in 2% hydroxypropyl methylcellulose pretreatment agent and stirred for 45 minutes. After removal, it is rinsed with distilled water to remove excess pretreatment agent from the surface; then, the copper-plated steel fiber is placed in a drying oven for drying at 70℃ for 2 hours. Step 1.2: Sulfuric acid and phosphoric acid are slowly added dropwise to deionized water and mixed evenly at room temperature to obtain a composite acid activator; Step 1.3: Put the recycled brick-mixed micro powder of various particle sizes, the kaolin of various particle sizes, the short-cut carbon fiber, the copper-plated steel fiber, and the graphite whiskers into a mixer and stir them. The stirring temperature is room temperature, the stirring speed is 200 rpm, and the stirring time is 6.5 min. Step 1.4: Place the electrolytic manganese dioxide and conductive carbon black into a mixer and continue stirring. The stirring temperature is room temperature, the stirring speed is 200 rpm, and the stirring time is 2.5 min. Step 1.5: Place the composite acid activator into a mixer and continue stirring at room temperature, 200 rpm, and for 3.5 minutes.

[0081] In step one, the preparation of the geopolymer electrolyte layer slurry includes the following steps in sequence: Step 2.1: Place the recycled brick-mixed micro powder and the metakaolin of each particle size into a drying oven for drying treatment. The drying temperature is 110℃ and the drying time is 7h. Step 2.2: Sulfuric acid and phosphoric acid are slowly added dropwise to deionized water and mixed evenly at room temperature to obtain a composite acid activator; Step 2.3: Put the recycled brick-mixed micro powder of various particle sizes, the metakaolin of various particle sizes, and the basalt fiber into a mixer and mix them. The mixing temperature is room temperature, the mixing speed is 200 rpm, and the mixing time is 6.5 min. Step 2.4: Put the potassium permanganate and foaming stabilizer from the foaming agent components into the mixer and continue to stir. The stirring temperature is room temperature, the stirring speed is 200 rpm, and the stirring time is 3 minutes. Step 2.5: Add hydrogen peroxide and compound acid activator from the foaming agent components to a mixer and continue stirring. The stirring temperature is room temperature, the stirring speed is 200 rpm, and the stirring time is 4 minutes.

[0082] In step one, the preparation of the geopolymer negative electrode slurry includes the following steps in sequence: Step 3.1: Place the recycled brick-mixed micro powder and the metakaolin of each particle size into a drying oven for drying treatment. The drying temperature is 110℃ and the drying time is 7h. First, the copper-plated steel fiber is immersed in 5% nitric acid for 15 minutes to remove the surface oxide layer; then, the copper-plated steel fiber is immersed in 2% hydroxypropyl methylcellulose pretreatment agent and stirred for 45 minutes. After removal, it is rinsed with distilled water to remove excess pretreatment agent from the surface; then, the copper-plated steel fiber is placed in a drying oven for drying at 70℃ for 2 hours. Step 3.2: Sulfuric acid and phosphoric acid are slowly added dropwise to deionized water and mixed evenly at room temperature to obtain a composite acid activator; Step 3.3: Place the recycled brick-mixed micro powder of various particle sizes, the metakaolin of various particle sizes, the zinc stearate coated aluminum powder, the short carbon fiber, the copper-plated steel fiber, and the graphite whiskers into a mixer and stir them. The stirring temperature is room temperature, the stirring speed is 200 rpm, and the stirring time is 6.5 min. Step 3.4: Place the electrolytic manganese dioxide and conductive carbon black into a mixer and continue stirring. The stirring temperature is room temperature, the stirring speed is 200 rpm, and the stirring time is 2.5 min. Step 3.5: Place the composite acid activator into a mixer and continue stirring at room temperature, 200 rpm, and for 3.5 minutes.

[0083] In steps two through four, the overall shape of the prepared geopolymer battery is a cube, and the height ratio of the geopolymer positive electrode layer, the geopolymer electrolyte layer, and the geopolymer negative electrode layer is 1:4.6:1.

[0084] In step two, the vibration and settling process of the geopolymer positive electrode layer is as follows: First, the geopolymer positive electrode layer slurry is poured into the molding mold according to the designed height ratio. The electric vibration table is started and the initial compaction is carried out at room temperature with a vibration frequency of 55Hz and a vibration time of 4min. Then, the electric vibration table is turned off and the mixture is left to stand naturally at room temperature for 25min with an ambient relative humidity of 25%.

[0085] In step three, the vibration and settling process of the geopolymer electrolyte layer is as follows: First, according to the designed height ratio, the geopolymer electrolyte layer slurry is poured onto the top of the geopolymer positive electrode layer in the molding mold. The electric vibration table is started, and preliminary compaction is performed at room temperature. The vibration frequency is 1.6 times the vibration frequency of the geopolymer positive electrode layer, and the vibration time is 1.9 times the vibration time of the geopolymer positive electrode layer. Then, the electric vibration table is turned off, and the mixture is allowed to stand naturally at room temperature for 35 minutes with an ambient relative humidity of 25%.

[0086] In step four, the vibration process of the geopolymer negative electrode layer is as follows: the geopolymer negative electrode layer slurry is poured onto the top of the geopolymer electrolyte layer in the molding mold according to the designed height ratio, the electric vibration table is started, and preliminary compaction is carried out at room temperature with a vibration frequency of 55Hz and a vibration time of 4min.

[0087] In step five, the process parameters for the directional arrangement of the copper-plated steel fibers are as follows: when vibration and magnetic field act together, the electromagnetic coil is a rectangular solenoid with an inner width of 25cm, a length of 95cm, and 550 turns. The electromagnetic coil operates under a 24V DC voltage with a working current of 3.5A, a magnetic field strength of not less than 30mT, a vibration frequency of 55Hz, and a duration of 6.5min for the combined action of vibration and magnetic field. When only the magnetic field acts, the duration of magnetic field action is 28min.

[0088] In step six, two curing processes are carried out, both at a temperature of 70℃ and with a relative humidity of no less than 95%. The first curing process lasts for 72 hours, and the second oxidation process lasts for 96 hours.

[0089] In step seven, the coating material is a silane impregnating agent with a thickness of 0.6 mm and a spraying pressure of 0.4 MPa.

[0090] The recycled brick-mixing powder, metakaolin, copper-plated steel fiber, and zinc stearate-coated aluminum powder used in this embodiment are as follows: Figures 1-4 As shown, the prepared geopolymer electrolyte layer slurry is as follows: Figure 5 As shown. In step five, after the copper-plated steel fibers are oriented and aligned, the overall structure formed by the three layers of slurry is as follows. Figure 6 As shown; in step six, the overall structure formed by the three layers of slurry after the second curing is as follows: Figure 7As shown; the microstructure of the geological polymer electrolyte layer is shown in the figure. Figure 8 As shown.

[0091] from Figure 7 It can be seen that after the three layers of grout are poured in sequence, and after vibration, static setting, and curing, the three layers of grout form a unified structure with strong interlayer bonding. From Figure 8 It can be seen that the internal pores of the electrolyte layer are uniform, and the internal pore structure is dominated by micropores with a concentrated pore size distribution. This is conducive to maintaining the capillary binding state of water in the electrolyte, thereby improving the water retention capacity of the electrolyte layer and enhancing its structural stability.

[0092] This embodiment has the following beneficial effects: the electrolyte has good stability; the geopolymer battery has excellent interlayer bonding force, conductivity and mechanical strength; the preparation process is simple, and the slurry of each layer can be mixed and poured according to the casting process.

[0093] Example 2: Another preferred embodiment of the acid-activated regenerated brick-concrete micropowder-metakaolin geopolymer battery and its preparation method according to the present invention is basically the same as that in Embodiment 1 in terms of material selection, preparation process, technical principle, and beneficial effects, except that: In the geopolymer positive electrode layer: the proportions of each substance in the geopolymer positive electrode layer are 39wt% recycled brick-mixed micro powder, 10wt% metakaolin, 35wt% conductive material, 12wt% composite acid, and 4wt% deionized water.

[0094] The recycled brick-mixed micro powder contains 80 wt% alumina and 6 wt% sodium oxide and potassium oxide, with an alumina to silica mass ratio of 1:1.2. The recycled brick-mixed micro powder has two particle size distributions: 20 wt% for particles 0.075 mm ≤ 0.5 mm and 80 wt% for particles 0 mm < 0.075 mm < 0.075 mm.

[0095] The metakaolin contains alumina and silica by a total mass of 90 wt%, and the mass ratio of alumina to silica is 1:1.2. The metakaolin has two particle size distributions: 5 μm ≤ particle size ≤ 10 μm accounts for 20 wt%, and 1 μm ≤ particle size < 5 μm accounts for 80 wt%.

[0096] The conductive material comprises 85 wt% electrolytic manganese dioxide, 11 wt% conductive carbon black, and 4 wt% conductive fiber; the conductive fiber consists of chopped carbon fiber, copper-plated steel fiber, and graphite whiskers in a mass ratio of 1.8:2.8:1. The composite acid consists of sulfuric acid and phosphoric acid in a mass ratio of 1:6.

[0097] In the geopolymer electrolyte layer: the proportions of each substance in the geopolymer electrolyte layer are as follows: 40wt% recycled brick-mixed micro powder, 10.5wt% metakaolin, 2wt% foaming agent, 1.5wt% foaming stabilizer, 3wt% basalt fiber, 33wt% composite acid, and 10wt% deionized water.

[0098] The recycled brick-mixed micro powder contains 80 wt% alumina and 6 wt% sodium oxide and potassium oxide, with an alumina to silica mass ratio of 1:1.2. The recycled brick-mixed micro powder has two particle size distributions: 20 wt% for particles 0.075 mm ≤ 0.5 mm and 80 wt% for particles 0 mm < 0.075 mm < 0.075 mm.

[0099] The metakaolin contains 90 wt% alumina and silica, with a mass ratio of 1:1.2. The metakaolin exhibits two particle size distributions: 20 wt% for particles 5 μm ≤ 10 μm and 80 wt% for particles 1 μm ≤ < 5 μm. The foaming agent contains hydrogen peroxide in a mass ratio of 1:1.5. The composite acid contains sulfuric acid in a mass ratio of 1:6.

[0100] In the geopolymer negative electrode layer: the proportions of each substance in the geopolymer negative electrode layer are as follows: 38wt% recycled brick-concrete micro powder, 10wt% metakaolin, 18wt% zinc stearate-coated aluminum powder, 10wt% conductive material, 18wt% composite acid, and 6wt% deionized water.

[0101] The recycled brick-mixed micro powder contains 80 wt% alumina and 6 wt% sodium oxide and potassium oxide, with an alumina to silica mass ratio of 1:1.2. The recycled brick-mixed micro powder has two particle size distributions: 20 wt% for particles 0.075 mm ≤ 0.5 mm and 80 wt% for particles 0 mm < 0.075 mm < 0.075 mm.

[0102] The metakaolin contains alumina and silica by a total mass of 90 wt%, and the mass ratio of alumina to silica is 1:1.2. The metakaolin has two particle size distributions: 5 μm ≤ particle size ≤ 10 μm accounts for 20 wt%, and 1 μm ≤ particle size < 5 μm accounts for 80 wt%.

[0103] The conductive material comprises 85 wt% electrolytic manganese dioxide, 11 wt% conductive carbon black, and 4 wt% conductive fiber; the conductive fiber consists of chopped carbon fiber, copper-plated steel fiber, and graphite whiskers in a mass ratio of 1.8:2.8:1. The composite acid consists of sulfuric acid and phosphoric acid in a mass ratio of 1:6.

[0104] In step one, the preparation method of the geopolymer positive electrode slurry includes the following main parameters: Step 1.1: The drying temperature for recycled brick-mixed micro powder of various particle sizes and kaolin of various particle sizes is 100℃ and the drying time is 8h; first, soak the copper-plated steel fiber in nitric acid for 10min, then soak it in hydroxypropyl methylcellulose pretreatment agent and stir for 30min; the drying temperature for the copper-plated steel fiber is 60℃ and the drying time is 2.5h. Step 1.3: The stirring speed of recycled brick-mixed micro powder of various particle sizes, kaolin of various particle sizes, short-cut carbon fiber, copper-plated steel fiber, and graphite whiskers is 100 rpm, and the stirring time is 8 min. Step 1.4: Add electrolytic manganese dioxide and conductive carbon black and continue stirring at 100 rpm for 3 minutes. Step 1.5: Add the compound acid activator and continue stirring at 100 rpm for 5 minutes.

[0105] In step one, the preparation method of the geopolymer electrolyte layer slurry includes the following main parameters: Step 2.1: The drying temperature for recycled brick-mixed micro powder of various particle sizes and kaolin of various particle sizes is 100℃ and the drying time is 8h. Step 2.3: The mixing speed of recycled brick-mixed micro powder of various particle sizes, kaolin of various particle sizes, and basalt fiber is 100 rpm, and the mixing time is 8 min; Step 2.4: Add potassium permanganate and foaming stabilizer and continue stirring at 100 rpm for 4 minutes. Step 2.5: Add hydrogen peroxide and compound acid activator and continue stirring at 100 rpm for 5 minutes.

[0106] In step one, the preparation method of the geopolymer negative electrode slurry includes the following main parameters: Step 3.1: The drying temperature for recycled brick-mixed micro powder of various particle sizes and kaolin of various particle sizes is 100℃ and the drying time is 8h; first, soak the copper-plated steel fiber in nitric acid for 10min, then soak it in hydroxypropyl methylcellulose pretreatment agent and stir for 30min; the drying temperature for the copper-plated steel fiber is 60℃ and the drying time is 2.5h. Step 3.3: The stirring speed of recycled brick-mixed micro powder of various particle sizes, metakaolin of various particle sizes, zinc stearate coated aluminum powder, short carbon fiber, copper-plated steel fiber, and graphite whiskers is 100 rpm, and the stirring time is 8 min. Step 3.4: Add electrolytic manganese dioxide and conductive carbon black and continue stirring at 100 rpm for 3 minutes. Step 3.5: Add the compound acid activator and continue stirring at 100 rpm for 5 minutes.

[0107] In steps two through four, the height ratio of the geopolymer positive electrode layer, the geopolymer electrolyte layer, and the geopolymer negative electrode layer is 1:4.2:1.

[0108] In step two, the vibration and settling process of the geopolymer positive electrode layer is as follows: the geopolymer positive electrode layer slurry is poured into the molding mold, initially compacted at room temperature with a vibration frequency of 50Hz and a vibration time of 5min; and then allowed to stand naturally at room temperature for 20min with an ambient relative humidity of 20%.

[0109] In step three, the vibration and settling process of the geopolymer electrolyte layer is as follows: the geopolymer electrolyte layer slurry is poured onto the top of the geopolymer positive electrode layer in the molding mold, and initially compacted at room temperature. The vibration frequency is 1.5 times that of the geopolymer positive electrode layer, and the vibration time is twice that of the geopolymer positive electrode layer. Then, it is left to stand naturally at room temperature for 20 minutes with a relative humidity of 20%.

[0110] In step four, the vibration process of the geopolymer negative electrode layer is as follows: the geopolymer negative electrode layer slurry is poured onto the geopolymer electrolyte layer in the molding mold, and initially compacted at room temperature with a vibration frequency of 50Hz and a vibration time of 5min.

[0111] In step five, the process parameters for the directional arrangement of the copper-plated steel fibers are as follows: when vibration and magnetic field act together, the inner width of the electromagnetic coil is 20cm, the length is 90cm, the number of coil turns is 500, the working current is 3A, the vibration frequency is 50Hz, and the duration of vibration and magnetic field acting together is 8min; when only magnetic field acts, the duration of magnetic field acting is 30min.

[0112] In step six, the curing temperature is 60℃ and the relative humidity is not lower than 95%. The first curing time is 72 hours and the second curing time is 96 hours.

[0113] In step seven, the coating thickness is 0.5 mm and the spraying pressure is 0.3 MPa.

[0114] Example 3: Another preferred embodiment of the acid-activated regenerated brick-concrete micropowder-metakaolin geopolymer battery and its preparation method according to the present invention is basically the same as that in Embodiment 1 in terms of material selection, preparation process, technical principle, and beneficial effects, except that: In the geopolymer positive electrode layer: the proportions of each substance in the geopolymer positive electrode layer are 44wt% recycled brick-mixed micro powder, 7wt% metakaolin, 25wt% conductive material, 17wt% composite acid, and 7wt% deionized water.

[0115] The recycled brick-mixed micro powder contains 90 wt% alumina and 4 wt% sodium oxide and potassium oxide, with an alumina to silica mass ratio of 1:1.5. The recycled brick-mixed micro powder has two particle size distributions: 30 wt% for particles 0.075 mm ≤ 0.5 mm and 70 wt% for particles 0 mm < 0.075 mm < 0.075 mm.

[0116] The metakaolin contains 95 wt% alumina and silica, with a mass ratio of 1:1.5. The metakaolin has two particle size distributions: 30 wt% for particles 5 μm ≤ 10 μm and 70 wt% for particles 1 μm ≤ < 5 μm.

[0117] The conductive material comprises 92 wt% electrolytic manganese dioxide, 6 wt% conductive carbon black, and 2 wt% conductive fiber; the conductive fiber consists of chopped carbon fiber, copper-plated steel fiber, and graphite whiskers in a mass ratio of 2.2:3.5:1. The composite acid consists of sulfuric acid and phosphoric acid in a mass ratio of 1:8.

[0118] In the geopolymer electrolyte layer: the proportions of each substance in the geopolymer electrolyte layer are as follows: 44wt% recycled brick-mixed micro powder, 12wt% metakaolin, 2.5wt% foaming agent, 2.2wt% foaming stabilizer, 2.3wt% basalt fiber, 29wt% composite acid, and 8wt% deionized water.

[0119] The recycled brick-mixed micro powder contains 90 wt% alumina and 4 wt% sodium oxide and potassium oxide, with an alumina to silica mass ratio of 1:1.5. The recycled brick-mixed micro powder has two particle size distributions: 30 wt% for particles 0.075 mm ≤ 0.5 mm and 70 wt% for particles 0 mm < 0.075 mm < 0.075 mm.

[0120] The metakaolin contains 95 wt% alumina and silica, with a mass ratio of 1:1.5. The metakaolin exhibits two particle size distributions: 30 wt% for particles 5 μm ≤ 10 μm and 70 wt% for particles 1 μm ≤ < 5 μm. The foaming agent contains hydrogen peroxide in a 1:2 mass ratio. The composite acid contains sulfuric acid in a 1:8 mass ratio.

[0121] In the geopolymer negative electrode layer: the proportions of each substance in the geopolymer negative electrode layer are as follows: 46 wt% recycled brick-concrete micro powder, 6 wt% metakaolin, 12 wt% zinc stearate coated aluminum powder, 20 wt% conductive material, 12 wt% composite acid, and 4 wt% deionized water.

[0122] The recycled brick-mixed micro powder contains 90 wt% alumina and 4 wt% sodium oxide and potassium oxide, with an alumina to silica mass ratio of 1:1.5. The recycled brick-mixed micro powder has two particle size distributions: 30 wt% for particles 0.075 mm ≤ 0.5 mm and 70 wt% for particles 0 mm < 0.075 mm < 0.075 mm.

[0123] The metakaolin contains 95 wt% alumina and silica, with a mass ratio of 1:1.5. The metakaolin has two particle size distributions: 30 wt% for particles 5 μm ≤ 10 μm and 70 wt% for particles 1 μm ≤ < 5 μm.

[0124] The conductive material comprises 92 wt% electrolytic manganese dioxide, 6 wt% conductive carbon black, and 2 wt% conductive fiber; the conductive fiber consists of chopped carbon fiber, copper-plated steel fiber, and graphite whiskers in a mass ratio of 2.2:3.5:1. The composite acid consists of sulfuric acid and phosphoric acid in a mass ratio of 1:8.

[0125] In step one, the preparation method of the geopolymer positive electrode slurry includes the following main parameters: Step 1.1: The drying temperature for recycled brick-mixed micro powder of various particle sizes and kaolin of various particle sizes is 120℃ and the drying time is 6h; first, soak the copper-plated steel fiber in nitric acid for 20min, then soak it in hydroxypropyl methylcellulose pretreatment agent and stir for 60min; the drying temperature for the copper-plated steel fiber is 80℃ and the drying time is 1.5h. Step 1.3: The stirring speed of recycled brick-mixed micro powder of various particle sizes, kaolin of various particle sizes, short-cut carbon fiber, copper-plated steel fiber, and graphite whiskers is 300 rpm, and the stirring time is 5 min. Step 1.4: Add electrolytic manganese dioxide and conductive carbon black and continue stirring at 300 rpm for 2 minutes. Step 1.5: Add the compound acid activator and continue stirring at 300 rpm for 2 minutes.

[0126] In step one, the preparation method of the geopolymer electrolyte layer slurry includes the following main parameters: Step 2.1: The drying temperature for recycled brick-mixed micro powder of various particle sizes and kaolin of various particle sizes is 120℃ and the drying time is 6h. Step 2.3: The mixing speed of recycled brick-mixed micro powder of various particle sizes, kaolin of various particle sizes, and basalt fiber is 300 rpm, and the mixing time is 5 min; Step 2.4: Add potassium permanganate and foaming stabilizer and continue stirring at 300 rpm for 2 minutes. Step 2.5: Add hydrogen peroxide and compound acid activator and continue stirring at 300 rpm for 3 minutes.

[0127] In step one, the preparation method of the geopolymer negative electrode slurry includes the following main parameters: Step 3.1: The drying temperature for recycled brick-mixed micro powder of various particle sizes and kaolin of various particle sizes is 120℃ and the drying time is 6h; first, soak the copper-plated steel fiber in nitric acid for 20min, then soak it in hydroxypropyl methylcellulose pretreatment agent and stir for 60min; the drying temperature for the copper-plated steel fiber is 80℃ and the drying time is 1.5h. Step 3.3: The stirring speed of recycled brick-mixed micro powder of various particle sizes, metakaolin of various particle sizes, zinc stearate coated aluminum powder, short carbon fiber, copper-plated steel fiber, and graphite whiskers is 300 rpm, and the stirring time is 5 min. Step 3.4: Add electrolytic manganese dioxide and conductive carbon black and continue stirring at 300 rpm for 2 minutes. Step 3.5: Add the compound acid activator and continue stirring at 300 rpm for 2 minutes.

[0128] In steps two through four, the height ratio of the geopolymer positive electrode layer, the geopolymer electrolyte layer, and the geopolymer negative electrode layer is 1:5:1.

[0129] In step two, the vibration and settling process of the geopolymer positive electrode layer is as follows: the geopolymer positive electrode layer slurry is poured into the molding mold, initially compacted at room temperature with a vibration frequency of 60Hz and a vibration time of 3min; and then allowed to stand naturally at room temperature for 30min with an ambient relative humidity of 30%.

[0130] In step three, the vibration and settling process of the geopolymer electrolyte layer is as follows: the geopolymer electrolyte layer slurry is poured onto the geopolymer positive electrode layer in the molding mold, and initially compacted at room temperature. The vibration frequency is 1.8 times that of the geopolymer positive electrode layer, and the vibration time is 1.8 times that of the geopolymer positive electrode layer. Then, it is left to stand naturally at room temperature for 40 minutes with an ambient relative humidity of 30%.

[0131] In step four, the vibration process of the geopolymer negative electrode layer is as follows: the geopolymer negative electrode layer slurry is poured onto the geopolymer electrolyte layer in the molding mold, and initially compacted at room temperature with a vibration frequency of 60Hz and a vibration time of 3min.

[0132] In step five, the process parameters for the directional arrangement of the copper-plated steel fibers are as follows: when vibration and magnetic field act together, the inner width of the electromagnetic coil is 30cm, the length is 100cm, the number of coil turns is 600, the working current is 4A, the vibration frequency is 60Hz, and the duration of vibration and magnetic field acting together is 5min; when only magnetic field acts, the duration of magnetic field acting is 25min.

[0133] In step six, the curing temperature is 80℃ and the relative humidity is not lower than 95%. The first curing time is 72 hours and the second curing time is 96 hours.

[0134] In step seven, the coating thickness is 0.8 mm and the spraying pressure is 0.6 MPa.

[0135] The performance of the geopolymer batteries prepared in the above three embodiments was tested. The test environment, test conditions, and test equipment were all the same. The test results are shown in Table 1.

[0136] As can be seen from the test results in Table 1, the geopolymer batteries prepared in the three examples possess both good electrical conductivity and mechanical properties. Each battery is square with a side length of 40 mm. A single battery can provide LED lighting for more than 11 minutes after a 5-minute charge. Depending on the actual application, several batteries can be connected in series.

[0137] The raw materials used in the above embodiments were purchased from Beijing Municipal Road and Bridge Building Materials Group Co., Ltd., Beijing Construction Engineering Group Co., Ltd., and Aladdin Reagent Co., Ltd., of which copper-plated steel fiber was purchased from Hengshui Berger Metal Products Co., Ltd., and zinc stearate coated aluminum powder was purchased from Qujing Huayixing New Materials Co., Ltd.

[0138] Special Note: The technical solution of this invention involves numerous parameters, and the synergistic effects between these parameters must be comprehensively considered to achieve the beneficial effects and significant progress of this invention. Furthermore, the value ranges of each parameter in the technical solution were obtained through extensive experimentation. For each parameter and the combinations thereof, the inventors have recorded a large amount of experimental data; however, due to space limitations, the specific experimental data is not disclosed here.

[0139] It will be readily understood by those skilled in the art that this invention includes any combination of the inventive description and specific embodiments outlined in the foregoing specification, as well as the various parts shown in the accompanying drawings. Due to space limitations and for the sake of brevity, not all of these combinations have been described in detail. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of this invention should be included within the scope of protection of this invention.

Claims

1. An acid-activated regenerated brick-concrete micro-powder-metakaolin geological polymer battery, characterized in that, The geopolymer battery is formed by sequentially stacking and casting a geopolymer positive electrode layer, a geopolymer electrolyte layer, and a geopolymer negative electrode layer, and is integrally cured and molded. The raw materials for preparing the geopolymer positive electrode layer, the geopolymer electrolyte layer, and the geopolymer negative electrode layer all include recycled brick-mixed micro powder and metakaolin, and the geopolymer slurry is prepared by acid activation.

2. The acid-activated regenerated brick-mixed micro-powder-metakaolin geopolymer battery according to claim 1, characterized in that, The mass percentage of each substance in the geopolymer positive electrode layer is as follows: 37-46 wt% recycled brick-mixed micro powder, 7-10 wt% metakaolin, 25-35 wt% conductive material, 12-18 wt% composite acid, and 4-8 wt% deionized water, with a total content of 100 wt%.

3. The acid-activated regenerated brick-mixed micro-powder-metakaolin geological polymer battery according to claim 2, characterized in that, In the geopolymer positive electrode layer: the recycled brick-concrete micro powder is a product obtained by processing construction waste generated from the demolition of brick-concrete buildings, and its brick-concrete content is not less than 90%; the chemical composition of the recycled brick-concrete micro powder is 80-90 wt% alumina and 4-6 wt% sodium oxide and potassium oxide, the mass ratio of alumina to silicon dioxide is 1:1.2-1.5, and the mass ratio of sodium oxide to potassium oxide is 1:1; The recycled brick-mixed powder comprises two particle sizes: 0.075mm ≤ particle size ≤ 0.5mm and 0mm < particle size < 0.075mm. The two particle sizes account for 20-30 wt% of the mass of the recycled brick-mixed powder, respectively, and 70-80 wt% of the mass of 0.075mm ≤ particle size ≤ 0.5mm and 0mm < particle size < 0.075mm. The metakaolin contains 90-95 wt% alumina and silica, with a mass ratio of 1:1.2-1.

5. The metakaolin comprises two particle sizes: 5 μm ≤ 10 μm and 1 μm ≤ < 5 μm. The two particle sizes account for 20-30 wt% of the total mass of the metakaolin, respectively, and 70-80 wt% of the particle size distribution (5 μm ≤ 10 μm and 1 μm ≤ < 5 μm). The conductive material comprises, by mass percentage, 85-92 wt% electrolytic manganese dioxide, 5-12 wt% conductive carbon black, and 1-5 wt% conductive fiber; the conductive fiber is composed of chopped carbon fiber, copper-plated steel fiber, and graphite whiskers, with a mass ratio of 1.8-2.2:2.8-3.5:

1. The electrolytic manganese dioxide has a particle size of no more than 75 μm; the conductive carbon black has a particle size controlled within the range of 10-20 nm; the short-cut carbon fibers have a diameter controlled within the range of 5-8 μm and a length controlled within the range of 3-5 mm; the copper-plated steel fibers have a diameter controlled within the range of 0.1-0.2 mm and a length controlled within the range of 3-5 mm, and the copper layer thickness controlled within the range of 1-3 μm; the graphite whiskers have a diameter controlled within the range of 0.5-1 μm and a length controlled within the range of 0.8-1.5 mm. The composite acid is composed of sulfuric acid and phosphoric acid, with the mass ratio of sulfuric acid to phosphoric acid being 1:6-8; the concentration of sulfuric acid is 60%, and the concentration of phosphoric acid is 85%.

4. The acid-activated regenerated brick-mixed micro-powder-metakaolin geopolymer battery according to claim 3, characterized in that, The mass percentage of each substance in the geopolymer electrolyte layer is as follows: 40-44 wt% recycled brick-mixed powder, 10-12 wt% metakaolin, 2-2.5 wt% foaming agent, 1.5-2.2 wt% foaming stabilizer, 2.2-3 wt% basalt fiber, 28-33 wt% composite acid, and 8-10 wt% deionized water, with a total content of 100 wt%.

5. The acid-activated regenerated brick-mixed micro-powder-metakaolin geological polymer battery according to claim 4, characterized in that, In the geopolymer electrolyte layer: the recycled brick-concrete micro powder is a product obtained by processing construction waste generated from the demolition of brick-concrete buildings, and its brick-concrete content is not less than 90%; the chemical composition of the recycled brick-concrete micro powder is 80-90 wt% alumina and 4-6 wt% sodium oxide and potassium oxide, the mass ratio of alumina to silicon dioxide is 1:1.2-1.5, and the mass ratio of sodium oxide to potassium oxide is 1:1; The recycled brick-mixed powder comprises two particle sizes: 0.075mm ≤ particle size ≤ 0.5mm and 0mm < particle size < 0.075mm. The two particle sizes account for 20-30 wt% of the mass of the recycled brick-mixed powder, respectively, and 70-80 wt% of the mass of 0.075mm ≤ particle size ≤ 0.5mm and 0mm < particle size < 0.075mm. The metakaolin contains 90-95 wt% alumina and silica, with a mass ratio of 1:1.2-1.

5. The metakaolin comprises two particle sizes: 5 μm ≤ 10 μm and 1 μm ≤ < 5 μm. The two particle sizes account for 20-30 wt% of the total mass of the metakaolin, respectively, and 70-80 wt% of the particle size distribution (5 μm ≤ 10 μm and 1 μm ≤ < 5 μm). The foaming agent is composed of hydrogen peroxide and potassium permanganate, and the mass ratio of hydrogen peroxide to potassium permanganate is 1:1.5-2; the foaming stabilizer is calcium stearate; the diameter of the basalt fiber is controlled within the range of 15-25 μm and the length is controlled within the range of 3-6 mm. The composite acid is composed of sulfuric acid and phosphoric acid, with the mass ratio of sulfuric acid to phosphoric acid being 1:6-8; the concentration of sulfuric acid is 60%, and the concentration of phosphoric acid is 85%.

6. The acid-activated regenerated brick-mixed micro-powder-metakaolin geopolymer battery according to claim 5, characterized in that, The mass percentage of each substance in the geopolymer negative electrode layer is as follows: 38-46 wt% recycled brick-mixed micro powder, 6-10 wt% metakaolin, 12-18 wt% zinc stearate-coated aluminum powder, 10-20 wt% conductive material, 12-18 wt% composite acid, and 4-6 wt% deionized water, with a total content of 100 wt%.

7. The acid-activated regenerated brick-mixed micro-powder-metakaolin geopolymer battery according to claim 6, characterized in that, In the geopolymer negative electrode layer: the recycled brick-concrete micro powder is a product obtained by processing construction waste generated from the demolition of brick-concrete buildings, and its brick-concrete content is not less than 90%; the chemical composition of the recycled brick-concrete micro powder is 80-90 wt% alumina and 4-6 wt% sodium oxide and potassium oxide, the mass ratio of alumina to silicon dioxide is 1:1.2-1.5, and the mass ratio of sodium oxide to potassium oxide is 1:1; The recycled brick-mixed powder comprises two particle sizes: 0.075mm ≤ particle size ≤ 0.5mm and 0mm < particle size < 0.075mm. The two particle sizes account for 20-30 wt% of the mass of the recycled brick-mixed powder, respectively, and 70-80 wt% of the mass of 0.075mm ≤ particle size ≤ 0.5mm and 0mm < particle size < 0.075mm. The metakaolin contains 90-95 wt% alumina and silica, with a mass ratio of 1:1.2-1.

5. The metakaolin comprises two particle sizes: 5 μm ≤ 10 μm and 1 μm ≤ < 5 μm. The two particle sizes account for 20-30 wt% of the total mass of the metakaolin, respectively, and 70-80 wt% of the particle size distribution (5 μm ≤ 10 μm and 1 μm ≤ < 5 μm). The particle size of the zinc stearate-coated aluminum powder is no greater than 10 μm, the thickness of the zinc stearate layer is no greater than 1 μm, and the particle size of the aluminum powder is controlled within the range of 100-200 nm. The conductive material comprises, by mass percentage, 85-92 wt% electrolytic manganese dioxide, 5-12 wt% conductive carbon black, and 1-5 wt% conductive fiber; the conductive fiber is composed of chopped carbon fiber, copper-plated steel fiber, and graphite whiskers, with a mass ratio of 1.8-2.2:2.8-3.5:

1. The electrolytic manganese dioxide has a particle size of no more than 75 μm; the conductive carbon black has a particle size controlled within the range of 10-20 nm; the short-cut carbon fibers have a diameter controlled within the range of 5-8 μm and a length controlled within the range of 3-5 mm; the copper-plated steel fibers have a diameter controlled within the range of 0.1-0.2 mm and a length controlled within the range of 3-5 mm, and the copper layer thickness controlled within the range of 1-3 μm; the graphite whiskers have a diameter controlled within the range of 0.5-1 μm and a length controlled within the range of 0.8-1.5 mm. The composite acid is composed of sulfuric acid and phosphoric acid, with the mass ratio of sulfuric acid to phosphoric acid being 1:6-8; the concentration of sulfuric acid is 60%, and the concentration of phosphoric acid is 85%.

8. A method for preparing an acid-activated regenerated brick-concrete micropowder-metakaolin geopolymer battery according to any one of claims 1-7, characterized in that, The preparation method includes the following steps in sequence: Step 1: Prepare geopolymer positive electrode slurry, geopolymer electrolyte slurry, and geopolymer negative electrode slurry according to the designed material ratio, and set them aside after preparation; Step 2: Fix the electromagnetic coil horizontally on the electric vibration table, and then place the molding mold horizontally inside the working area of ​​the electromagnetic coil; according to the designed height ratio of the geopolymer positive electrode layer, geopolymer electrolyte layer and geopolymer negative electrode layer, pour the geopolymer positive electrode layer slurry into the molding mold, and then vibrate and let it stand in sequence to form the geopolymer positive electrode layer. Step 3: According to the designed height ratio of the geopolymer positive electrode layer, geopolymer electrolyte layer and geopolymer negative electrode layer, pour the geopolymer electrolyte layer slurry onto the geopolymer positive electrode layer in the molding mold, and then vibrate and let it stand in sequence to form the geopolymer electrolyte layer. Step 4: According to the designed height ratio of the geopolymer positive electrode layer, geopolymer electrolyte layer and geopolymer negative electrode layer, pour the geopolymer negative electrode layer slurry onto the top of the geopolymer electrolyte layer in the molding mold, and then vibrate it to form the geopolymer negative electrode layer. Step 5: The electric vibration table continues to vibrate, and the electromagnetic coil is turned on at the same time. Under the combined action of vibration and magnetic field, the copper-plated steel fibers in the overall structure composed of the geopolymer positive electrode layer, the geopolymer electrolyte layer and the geopolymer negative electrode layer gradually align laterally along the direction of magnetic induction lines. After the vibration reaches the preset time, the electric vibration table stops vibrating, and the electromagnetic coil continues to work, further enabling the copper-plated steel fibers to complete the directional alignment along the direction of magnetic induction lines. Step Six: Seal the molding mold and its internal structure with plastic film, and place it in a curing box for the first curing. After the first curing is completed, demold the mold, seal the entire structure with plastic film, and place it in the curing box again for the second curing. After the second curing is completed, remove the plastic film; attach conductive metal sheets to the sides of the geopolymer positive electrode layer and the geopolymer negative electrode layer respectively. Step 7: Apply a coating to the outer surface of the overall structure after removing the plastic film using a spray gun to obtain the acid-activated regenerated brick-concrete micro-powder-metakaolin geological polymer battery.

9. The preparation method of the acid-activated regenerated brick-concrete micro-powder-metakaolin geological polymer battery according to claim 8, characterized in that, In step one, the preparation of the geopolymer positive electrode slurry includes the following steps in sequence: Step 1.1: Place the recycled brick-mixed micro powder and the kaolin of each particle size into a drying oven for drying treatment. The drying temperature is 100-120℃ and the drying time is 6-8h. First, immerse the copper-plated steel fiber in 5% nitric acid for 10-20 minutes to remove the surface oxide layer; then immerse the copper-plated steel fiber in 2% hydroxypropyl methylcellulose pretreatment agent and stir for 30-60 minutes. After removal, rinse with distilled water to remove excess pretreatment agent from the surface; then place the copper-plated steel fiber in a drying oven for drying at 60-80℃ for 1.5-2.5 hours. Step 1.2: Sulfuric acid and phosphoric acid are slowly added dropwise to deionized water and mixed evenly at room temperature to obtain a composite acid activator; Step 1.3: Put the recycled brick-mixed micro powder of various particle sizes, the kaolin of various particle sizes, the short-cut carbon fiber, the copper-plated steel fiber, and the graphite whiskers into a mixer and stir them. The stirring temperature is room temperature, the stirring speed is 100-300 rpm, and the stirring time is 5-8 minutes. Step 1.4: Place the electrolytic manganese dioxide and conductive carbon black into a mixer and continue stirring. The stirring temperature is room temperature, the stirring speed is 100-300 rpm, and the stirring time is 2-3 minutes. Step 1.5: Place the composite acid activator into a mixer and continue stirring. The stirring temperature is room temperature, the stirring speed is 100-300 rpm, and the stirring time is 2-5 minutes. In step one, the preparation of the geopolymer electrolyte layer slurry includes the following steps in sequence: Step 2.1: Place the recycled brick-mixed micro powder and the kaolin of each particle size into a drying oven for drying treatment. The drying temperature is 100-120℃ and the drying time is 6-8h. Step 2.2: Sulfuric acid and phosphoric acid are slowly added dropwise to deionized water and mixed evenly at room temperature to obtain a composite acid activator; Step 2.3: Put the recycled brick-mixed micro powder of various particle sizes, the kaolin of various particle sizes, and the basalt fiber into a mixer and mix them. The mixing temperature is room temperature, the mixing speed is 100-300 rpm, and the mixing time is 5-8 minutes. Step 2.4: Put the potassium permanganate and foaming stabilizer from the foaming agent components into the mixer and continue to stir. The stirring temperature is room temperature, the stirring speed is 100-300 rpm, and the stirring time is 2-4 min. Step 2.5: Add hydrogen peroxide and compound acid activator from the foaming agent components to a mixer and continue stirring. The stirring temperature is room temperature, the stirring speed is 100-300 rpm, and the stirring time is 3-5 minutes. In step one, the preparation of the geopolymer negative electrode slurry includes the following steps in sequence: Step 3.1: Place the recycled brick-mixed micro powder and the kaolin of each particle size into a drying oven for drying treatment. The drying temperature is 100-120℃ and the drying time is 6-8h. First, immerse the copper-plated steel fiber in 5% nitric acid for 10-20 minutes to remove the surface oxide layer; then immerse the copper-plated steel fiber in 2% hydroxypropyl methylcellulose pretreatment agent and stir for 30-60 minutes. After removal, rinse with distilled water to remove excess pretreatment agent from the surface; then place the copper-plated steel fiber in a drying oven for drying at 60-80℃ for 1.5-2.5 hours. Step 3.2: Sulfuric acid and phosphoric acid are slowly added dropwise to deionized water and mixed evenly at room temperature to obtain a composite acid activator; Step 3.3: Put the recycled brick-mixed micro powder of various particle sizes, the metakaolin of various particle sizes, zinc stearate coated aluminum powder, short carbon fiber, copper-plated steel fiber, and graphite whiskers into a mixer and stir them. The stirring temperature is room temperature, the stirring speed is 100-300 rpm, and the stirring time is 5-8 minutes. Step 3.4: Place the electrolytic manganese dioxide and conductive carbon black into a mixer and continue stirring. The stirring temperature is room temperature, the stirring speed is 100-300 rpm, and the stirring time is 2-3 minutes. Step 3.5: Place the composite acid activator into a mixer and continue stirring. The stirring temperature is room temperature, the stirring speed is 100-300 rpm, and the stirring time is 2-5 minutes.

10. The preparation method of the acid-activated regenerated brick-concrete micro-powder-metakaolin geopolymer battery according to claim 8, characterized in that, In steps two to four, the overall shape of the prepared geopolymer battery includes any one of cube, cuboid, and cylindrical shapes, and the height ratio of the geopolymer positive electrode layer, the geopolymer electrolyte layer, and the geopolymer negative electrode layer is 1:4.2-5:

1. In step two, the vibration and settling process of the geopolymer positive electrode layer is as follows: First, the geopolymer positive electrode layer slurry is poured into the molding mold according to the designed height ratio. The electric vibration table is started, and preliminary compaction is performed at room temperature with a vibration frequency of 50-60Hz and a vibration time of 3-5 minutes. Then, the electric vibration table is turned off, and the mixture is allowed to stand naturally at room temperature for 20-30 minutes with an ambient relative humidity of 20-30%. In step three, the vibration and settling process of the geopolymer electrolyte layer is as follows: First, according to the designed height ratio, the geopolymer electrolyte layer slurry is poured onto the top of the geopolymer positive electrode layer in the molding mold. The electric vibration table is started, and preliminary compaction is performed at room temperature. The vibration frequency is 1.5-1.8 times the vibration frequency of the geopolymer positive electrode layer, and the vibration time is 1.8-2 times the vibration time of the geopolymer positive electrode layer. Then, the electric vibration table is turned off, and the mixture is allowed to stand naturally at room temperature for 30-40 minutes with a relative humidity of 20-30%. In step four, the vibration process of the geopolymer negative electrode layer is as follows: according to the designed height ratio, the geopolymer negative electrode layer slurry is poured onto the top of the geopolymer electrolyte layer in the molding mold, the electric vibration table is started, and preliminary compaction is carried out at room temperature with a vibration frequency of 50-60Hz and a vibration time of 3-5min. In step five, the process parameters for the directional arrangement of the copper-plated steel fibers are as follows: when vibration and magnetic field act together, the electromagnetic coil is a rectangular solenoid with an inner width of 20-30cm, a length of 90-100cm, and 500-600 turns. The electromagnetic coil operates under a 24V DC voltage with a working current of 3-4A, a magnetic field strength of not less than 30mT, a vibration frequency of 50-60Hz, and a duration of combined vibration and magnetic field action of 5-8min; when only the magnetic field acts, the duration of magnetic field action is 25-30min. In step six, two curing processes are carried out, with a curing temperature of 60-80℃ and an ambient relative humidity of not less than 95%. The first curing process lasts for 72 hours, and the second curing process lasts for 96 hours. In step seven, the coating material is a silane impregnating agent with a thickness of 0.5-0.8 mm and a spraying pressure of 0.3-0.6 MPa.

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