Cement-based structural battery integrating load-bearing and energy-storage functions, and preparation method therefor

Abstract

The present invention relates to the technical field of cement-based batteries for construction. Disclosed are a cement-based structural battery integrating load-bearing and energy-storage functions, and a preparation method therefor. The method comprises: 1) mixing a polymer solution, cement, and fine sand to obtain a polymer-cement paste electrolyte; wherein the polymer solution is obtained by dissolving a polymer and a strong alkali in water, or by dissolving a polymer, a strong alkali, and a sulfide in water, or by dissolving a polymer, a strong alkali, an inorganic sulfide, and a chemical cross-linking agent in water; and the polymer is one or more of PVA or PAA; 2) preparing a positive electrode sheet; 3) preparing a negative electrode sheet; and 4) placing the polymer-cement paste electrolyte on a surface of the positive electrode sheet and a surface of the negative electrode sheet, then sequentially stacking the positive electrode sheet and the negative electrode sheet, and placing the stack in a mold for curing and allowing the stack to stand, so as to obtain a cement-based structural battery integrating load-bearing and energy-storage functions. The cement-based structural battery of the present invention has high mechanical load-bearing strength, high capacity, stable charge retention, and excellent cycling performance.

Description

A cement-based structural battery integrating load-bearing and energy storage and its preparation method Technical Field

[0001] This invention belongs to the technical field of cement-based batteries for building applications, specifically relating to a cement-based structural battery that integrates load-bearing and energy storage and its preparation method. Background Technology

[0002] To address the depletion and pollution issues of traditional energy sources, the application of new energy sources such as solar and wind power has increased dramatically. However, the intermittency and volatility of these new energy sources have led to a mismatch between energy supply and demand, necessitating energy storage materials and equipment to store the electricity generated by these sources. Future advanced building materials should possess multifunctional intelligent characteristics, such as the ability to collect and store renewable energy sources like solar and wind power. Using structures and buildings as energy and storage devices has significant innovative implications. Due to the large volume of buildings, even if the energy density per unit volume of next-generation building materials is not high, their energy storage potential is considerable. However, the low ion conductivity, high resistance, and lack of electrodes suitable for the cement environment inherent in traditional cement have led current development trends in cement-based structural energy storage materials to focus on cement-based supercapacitors. The low energy density and poor charge retention of supercapacitors severely limit the application of cement-based structured energy storage materials in buildings. Achieving cement-based structural batteries that combine high mechanical strength, high capacity, stable charge retention, and excellent cycle life remains extremely difficult.

[0003] Therefore, cement-based structural batteries need further development. Summary of the Invention

[0004] Given the current lack of cement-based battery technology, the purpose of this invention is to provide a cement-based battery that integrates load-bearing and energy storage, as well as its preparation method. The cement-based battery of this invention possesses high mechanical load-bearing strength, high capacity, stable charge retention, and excellent cycle life.

[0005] The technical solution of the present invention is as follows:

[0006] A method for fabricating a cement-based structured battery that integrates load-bearing and energy storage includes the following steps:

[0007] 1) The polymer solution, cement, and fine sand are mixed to obtain a polymer-cement paste electrolyte;

[0008] The polymer solution is obtained by dissolving a polymer and a strong base in water, or by dissolving a polymer, a strong base, and a sulfide in water, or by dissolving a polymer, a strong base, an inorganic sulfide, and a chemical crosslinking agent in water.

[0009] The polymer is one or more of PVA or PAA; the strong base is one or more of KOH or NaOH; the sulfide is one or more of Na2S or K2S; the chemical crosslinking agent is one or more of TEAC (tetraethylammonium chloride) or PEGDGE (polyethylene glycol diglycidyl ether).

[0010] 2) Preparation of the positive electrode sheet;

[0011] 3) Preparation of the negative electrode sheet;

[0012] 4) The polymer-cement slurry electrolyte is placed on the surface of the positive electrode and the surface of the negative electrode, respectively. Then the positive electrode and the negative electrode are stacked in sequence, placed in a mold for curing, and left to stand to obtain a cement-based structure battery that integrates load-bearing and energy storage.

[0013] The amounts of each substance in the polymer solution described in step 1) are, by weight:

[0014] 8-10 parts of polymer

[0015] 30-40 parts of strong alkali

[0016] 190-210 parts water;

[0017] When inorganic sulfides are present, the amount of sulfide used is 0.5-1 part;

[0018] When a chemical crosslinking agent is present, the amount of the chemical crosslinking agent is 0.1-0.5 parts.

[0019] The mixing described in step 1) specifically involves mixing a solution of polymer and strong alkali, cement and fine sand at 90-95°C, then cooling it to 2-5°C, and slowly adding cold water during the cooling process to obtain a cement paste containing a liquid-solid mixed phase.

[0020] When the polymer solution contains inorganic sulfides, the inorganic sulfides are added together with the aforementioned cold water; when the polymer solution contains chemical crosslinking agents, the chemical crosslinking agents are added together with the aforementioned cold water.

[0021] The cement slurry containing the liquid-solid mixed phase is prepared under stirring conditions, with a stirring speed of 135-165 r / min.

[0022] The mixing time at 90-95℃ is 1-2 minutes; the cooling to 2-5℃ means cooling to 2-5℃ in 5-10 minutes; after adding cold water and cooling to 2-5℃, stir and mix for 15-20 minutes.

[0023] The process of mixing the polymer and strong alkali solution, cement, and fine sand at 90-95°C refers to: stirring the polymer, strong alkali, and water at 85-95°C at a speed of 240-260 r / min for 1.5-2 hours to prepare a solution; dry mixing the cement and fine sand at 90-95°C at a speed of 60-70 r / min for 5-10 minutes to obtain a cement-fine sand mixture; and then mixing the above solution and cement-fine sand mixture at 90-95°C.

[0024] The solution prepared by polymer and strong base refers to the process of stirring the polymer and a portion of water at 85-95℃ and a speed of 240-260 r / min for 40-50 min to obtain an aqueous solution of polymer; dissolving the strong base in another portion of water to obtain a strong base solution; and mixing the strong base solution with the aqueous solution of polymer for 50-70 min while keeping the temperature and speed constant to obtain the desired solution.

[0025] The mass ratio of cold water to polymer is (60-80):(8-10).

[0026] The amounts of polymer, cement, and fine sand in the polymer solution described in step 1) are as follows by weight: polymer: 8-10 parts; cement: 490-510 parts; fine sand: 140-160 parts.

[0027] The polymer PVA has a molecular weight of 1,000-10,000, and the PAA has a molecular weight of 10,000-500,000.

[0028] The positive electrode sheet mentioned in step 2) is prepared by the following method:

[0029] S1: Mix the positive electrode material, conductive agent, binder and solvent evenly to obtain a positive electrode active material slurry; S2: Coat the positive electrode active material slurry onto the surface of the conductive substrate, form a film and then dry it to obtain a positive electrode sheet.

[0030] The cathode material is one or more of nickel hydroxide, transition metals (e.g., cobalt), transition metal oxides (cobalt oxides), and transition metal hydroxides.

[0031] The conductive agent is one or more of graphite and carbon nanotubes.

[0032] The adhesive is potassium silicate or sodium silicate. The modulus of the silicate is 2.0-3.3.

[0033] The solvent is water.

[0034] The mass ratio of the positive electrode material, conductive agent and binder is (8-9.5):(0.5-1):(3-6).

[0035] The mass ratio of the positive electrode material to the solvent is (8-9.5):(0.4-0.8). The coating amount of the positive electrode active material slurry is 0.3-0.4 g / cm³. 2 The positive electrode active material slurry is coated on both surfaces of the conductive substrate.

[0036] The conductive agent is divided into two parts: one part is mixed with the positive electrode material, and the other part is mixed with the binder and solvent.

[0037] The conductive substrate is a metal sheet such as nickel foam, copper foil, or aluminum foil.

[0038] The negative electrode sheet described in step 3) is prepared by the following method: the negative electrode active material, conductive agent and binder are uniformly mixed to obtain a negative electrode active material slurry; the negative electrode active material slurry is coated on the surface of a conductive substrate, and after film formation, it is dried to obtain a negative electrode sheet.

[0039] The negative electrode active material is one or more of the following: iron, iron oxide, iron(II,III) oxide, iron carbonyl, ferrous sulfide, bismuth sulfide, zinc, zinc oxide, zinc-containing alloys, and iron-containing alloys.

[0040] The conductive agent is one or more of carbon nanotubes and graphite.

[0041] The adhesive is one or more of potassium silicate and sodium silicate.

[0042] The coating amount of the negative electrode active material slurry is 0.35-0.45 g / cm³. 2 .

[0043] The mass ratio of the negative electrode active material, conductive agent, and binder is (7.5-10):(0-0.5):(3-5.5).

[0044] The conductive substrate is a metal sheet such as nickel foam, copper foil, or aluminum foil.

[0045] The curing mentioned in step 4) refers to curing in a sealed environment at 0℃-3℃ for 6-24 hours. The static setting refers to 12-24 hours at room temperature.

[0046] A cement-based structured battery integrating load-bearing and energy storage was prepared by the above-described method.

[0047] The application of the battery of this invention in construction. Beneficial effects:

[0048] 1) This invention employs controlled phase separation technology, which enables the elastic phase separation of the polymer-strong alkali network (e.g., PVA-KOH) network to occur earlier than cement hydration. During the hydration process, cement adaptively becomes the framework of the polymer-strong alkali network, and the interface between the two is good, which can form continuous high-flux ion channels.

[0049] 2) The positive and negative electrodes of this invention use water glass as a binder. Due to its good compatibility, it can form a strong electrolyte-electrode interface, which greatly improves the conductivity of ions at the interface.

[0050] 3) The preparation process of this invention is simple to operate, highly repeatable, and the raw materials used are environmentally friendly and inexpensive.

[0051] In summary, the cement-based structure battery of the present invention combines high mechanical load-bearing strength, high capacity, stable charge retention, and excellent cycle performance. Attached Figure Description

[0052] Figure 1 is a schematic diagram of the structure of the cement-based battery of the present invention; 1-positive electrode, 2-negative electrode, 3-electrolyte, 4-lead-out portion (current collector) of the substrate; the top two figures are schematic cross-sectional views, and the bottom figure is a top view;

[0053] Figure 2 is a schematic diagram of the preparation of cement-based structure battery using a mold with circular components according to the present invention; 5- Circular component 1 of the mold, 6- Semi-circular component 2 of the mold, 7- Positive electrode, 8- Negative electrode;

[0054] Figure 3 is a schematic diagram of the preparation of cement-based structure battery using a square component mold according to the present invention; 9-square component 1 of the mold, 10-right-angled triangular component 2 of the mold, 11-positive electrode, 12-negative electrode;

[0055] Figure 4 shows the EIS (Nyquist plot) of the battery prepared in Example 1;

[0056] Figure 5 shows the EIS of the battery prepared in Example 2;

[0057] Figure 6 shows the EIS of the battery prepared in Example 3;

[0058] Figure 7 shows the EIS of the battery prepared in Comparative Example 1;

[0059] Figure 8 shows the EIS of the battery prepared in Comparative Example 2;

[0060] Figure 9 shows the EIS of the battery prepared in Comparative Example 3;

[0061] Figure 10 shows the LSV curves of the batteries prepared in Example 1, Comparative Examples 1 and 3.

[0062] Figure 11 shows the CV curves of the batteries prepared in Example 1, Comparative Examples 1 and 3.

[0063] Figure 12 shows the XRD pattern of the positive electrode prepared in Example 1;

[0064] Figure 13 is the XRD pattern of the negative electrode prepared in Example 1;

[0065] Figure 14 shows the voltage-discharge capacity curves of the batteries prepared in Examples 1-3;

[0066] Figure 15 is a voltage-discharge capacity curve of the battery prepared in Example 4;

[0067] Figure 16 shows the voltage-discharge capacity curves of the batteries prepared in Comparative Examples 1 to 3.

[0068] Figure 17 shows the charge-discharge cycle performance test results of the battery prepared in Example 1;

[0069] Figure 18 shows the charge retention performance test curves of Examples 1 and 2 and commercial nickel-iron batteries;

[0070] Figure 19 shows the LEDs lit by the batteries prepared in Examples 5 and 6 after being connected in series. Detailed Implementation

[0071] The present invention will be further described in detail below with reference to specific embodiments, but the implementation of the present invention is not limited thereto.

[0072] Figure 1 is a schematic diagram of the cement-based structural battery of the present invention; the top two figures are schematic cross-sectional views, and the bottom figure is a top view. The cement-based structural battery of the present invention includes a positive electrode and a negative electrode, and an electrolyte covering the positive and negative electrode. The positive and negative electrode are stacked sequentially, and the electrolyte is disposed between the positive and negative electrode. The positive and negative electrode are respectively provided with lead-out portions of the substrate, i.e., current collectors.

[0073] Figure 2 is a schematic diagram of the preparation of a cement-based structure battery using a mold with circular components according to the present invention. The mold of the present invention includes two components 1 and four semi-circular components 2. The two semi-circular components 2 can be assembled into a circular component 3, which is hollow, while component 1 is a solid circular component. The two circular components 3 are stacked sequentially, forming a hollow center. Component 1 is located at both ends of the stacked circular components 3, sealing the ports. The positive electrode is located in one circular component 3, and the negative electrode is located in another circular component 3. Electrolytes are provided in the cavities of the circular components 3 between the negative and positive electrodes.

[0074] Figure 3 is a schematic diagram of the cement-based structure battery fabricated using a mold with square components according to the present invention. The mold of the present invention includes two square components (1) and four right-angled triangular components (2). The two right-angled triangular components (2) can be assembled into a square component (3), which is hollow, while component 1 is a solid square component. The two square components (3) are stacked sequentially, forming a hollow space in the middle. Component 1 is located at both ends of the stacked square components (3), sealing the ports. The positive electrode is located in the square component (3), and the negative electrode is located in another square component (3). Electrolytes are provided between the negative and positive electrodes and in the cavities of the square components (3).

[0075] Example 1: (Polymer solution is PVA-KOH)

[0076] Dissolve 10g of PVA1799 in 90g of deionized water, heat in a 95℃ water bath and stir at 250r / min for 50min to obtain a PVA solution; dissolve 30g of KOH solid in 110g of water to obtain a KOH solution; when the PVA solution turns a light milky white color, slowly add the KOH solution dropwise to the PVA solution while maintaining heating and stirring for 50min until the mixed solution turns transparent and light yellow to obtain a PK solution. Premix 490g of cement (PO42.5R) and 140g of fine sand at 70r / min for 10min at 90℃ to obtain a cement-fine sand mixture; while maintaining 90℃, add the cement-fine sand mixture to the PK solution and stir at 145r / min for 2min. After this process, turn on the cooler and slowly add 60g of deionized water at 2℃ to lower the slurry temperature to 2℃, and stir at 145r / min for 16min to obtain a polymer-cement slurry.

[0077] The positive electrode is prepared as follows: 0.36g Co and 8.7g Ni(OH) )2 Grind for 15 minutes until the powder turns dark green. Add 0.43g of 100-mesh graphite and continue grinding for 13 minutes until the powder turns grayish-green, obtaining a mixed powder. Weigh 4.3g of low-temperature potassium silicate with a modulus of 3.3, add 0.7g of deionized water and 0.28g of 100-mesh graphite, and stir until homogeneous to obtain a silicate dispersion. Add the mixed powder to the silicate dispersion in two batches, stirring until a homogeneous slurry is formed. Coat the slurry evenly onto a 2mm*2mm square clean nickel foam substrate (0.35g / cm²). 2 After the electrode film is formed, place it under a 320W drying light source for 30 minutes until the electrode surface turns dark green and the center of the area hardens, then seal and bag it.

[0078] The negative electrode is prepared as follows: 0.6g FeS and 6.8g iron powder are ground for 10 minutes until the powder is uniform. 2.1g Fe3O4 is added and grinding continues for 20 minutes until the powder turns dark orange, obtaining a mixed powder. The mixed powder is added in two portions to 4.55g of low-temperature potassium silicate with a modulus of 3.3, and stirred until a homogeneous slurry is formed. This slurry is then uniformly coated onto a 2mm*2mm square clean nickel foam substrate (0.4g / cm²). 2 After coating the electrode, let it stand for 13 minutes until a film forms on the electrode surface. Then, place it under a 320W drying light source for 27 minutes until the center of the electrode area hardens. Finally, seal and bag it.

[0079] The positive and negative electrode sheets were assembled using polymer-cement slurry (that is, the polymer-cement slurry was coated on the surface of the positive and negative electrode sheets respectively), placed in a mold, and cured in a sealed environment at 2°C for 24 hours, and then left to stand at room temperature for 24 hours to obtain a cement-based structured battery.

[0080] Example 2: (Polymer solution is PVA-PAA-KOH)

[0081] 7.8g PVA1799 and 0.2g PAA (polyacrylic acid, molecular weight 450,000) were dissolved in 90g deionized water, heated in an 85°C water bath and stirred at 260r / min for 50min to obtain a polymer solution. 40g KOH solid was dissolved in 115g water to obtain a KOH solution. When the polymer solution turned a light milky white color, the KOH solution was slowly added dropwise to the polymer solution while maintaining heating and stirring for 70min to obtain a PKA solution. 510g cement (PO42.5R) and 160g fine sand were premixed at 65r / min for 8min at 95°C to obtain a cement-fine sand mixture. The cement-fine sand mixture was added to the PKA solution while maintaining 95°C and stirring at 140r / min for 1min30s. After this process, the cooler was turned on and 80g deionized water at 5°C was slowly added to lower the slurry temperature to 5°C. The mixture was stirred at 140r / min for 20min to obtain a polymer-cement slurry.

[0082] The positive electrode is prepared as follows: 0.40g Co and 8.0g Ni(OH)2 are ground for 15 minutes until the powder is dark green. 0.43g of 100-mesh graphite is added, and grinding continues for 13 minutes until the powder is grayish-green, obtaining a mixed powder. 4.3g of low-temperature potassium silicate with a modulus of 3.3 is weighed, and 0.7g of deionized water and 0.25g of 100-mesh graphite are added and stirred until homogeneous, obtaining a potassium silicate mixture. The mixed powder is added to the potassium silicate mixture in two batches, stirring until a homogeneous slurry is formed. This slurry is then evenly coated onto a 2mm*2mm square clean nickel foam substrate (0.35g / cm²). 2 After the electrode film is formed, place it under a 320W drying light source for 28 minutes until the electrode surface turns dark green and the center of the area hardens, then seal and bag it.

[0083] The negative electrode is prepared as follows: 0.6g FeS and 6.8g iron powder are ground for 10 minutes until the powder is uniform. 2.1g Fe3O4 is added and grinding continues for 20 minutes to obtain a mixed powder. The mixed powder is added in two portions to 4.55g of low-temperature potassium silicate with a modulus of 3.3, and stirred until a homogeneous slurry is formed. This slurry is then uniformly coated onto a 2mm*2mm square clean nickel foam substrate (0.4g / cm²). 2After coating the electrode, let it stand for 15 minutes until a film forms on the electrode surface. Then, place it under a 320W drying light source for 27 minutes until the center of the electrode area hardens. Finally, seal and bag it.

[0084] Positive and negative electrode sheets were assembled using polymer-cement slurry, placed in a special mold, and cured in a sealed environment at 0°C for 6 hours, followed by standing at room temperature for 12 hours to obtain a cement-based structured battery.

[0085] Example 3: (Polymer solution is PVA-KOH-K2S)

[0086] Dissolve 9.8g of PVA1799 in 90g of deionized water, heat in a 92℃ water bath and stir at 255r / min for 4min to obtain a polymer solution; dissolve 33.6g of KOH solid in 110g of water to obtain a KOH solution. When the PVA solution turns a pale milky white color, slowly add the KOH solution dropwise to the PVA solution while maintaining heating and stirring for 50min to obtain a PK solution. Premix 500g of cement (PO42.5R) and 150g of fine sand at 60r / min for 5min at 92℃ to obtain a cement-fine sand mixture. Maintaining 92℃, add the cement-fine sand mixture to the PK solution and stir at 135r / min for 1min45s. After this process, turn on the cooler and slowly add 65g of deionized water at 3℃ and 0.8g of K2S to lower the slurry temperature to 3℃. Maintain stirring at 135r / min for 18min to obtain a polymer-cement slurry.

[0087] The positive electrode is prepared as follows: 0.36g Co and 8.7g Ni(OH)₂ are ground for 15 minutes until the powder is dark green. 0.43g of 100-mesh graphite is added, and grinding continues for 13 minutes until the powder is grayish-green, obtaining a mixed powder. 4.3g of low-temperature potassium silicate with a modulus of 3.3 is weighed, and 0.7g of deionized water and 0.28g of 100-mesh graphite are added and stirred until homogeneous, obtaining a potassium silicate mixture. The mixed powder is added to the potassium silicate mixture in two batches, stirring until a homogeneous slurry is formed. This slurry is then evenly coated onto a 2mm*2mm square clean nickel foam substrate (0.35g / cm²). 2 After the electrode film is formed, place it under a 320W drying light source for 30 minutes until the electrode surface turns dark green and the center of the area hardens, then seal and bag it.

[0088] The negative electrode is prepared as follows: 0.6g FeS and 6.8g iron powder are ground for 10 minutes until the powder is uniform. 2.1g Fe3O4 is added and grinding continues for 20 minutes to obtain a mixed powder. The mixed powder is added in two portions to 4.55g of low-temperature potassium silicate with a modulus of 3.3, and stirred until a homogeneous slurry is formed. This slurry is then uniformly coated onto a 2mm*2mm square clean nickel foam substrate (0.4g / cm²). 2After coating the electrode, let it stand for 15 minutes until a film forms on the electrode surface. Then, place it under a 320W drying light source for 29 minutes until the center of the electrode area hardens. Finally, seal and package it.

[0089] Positive and negative electrode sheets were assembled using polymer-cement slurry, placed in a special mold, and cured in a sealed environment at 1°C for 21 hours, followed by standing at room temperature for 18 hours to obtain a cement-based structured battery.

[0090] Example 4: (Polymer solution is PVA-KOH)

[0091] 10g of PVA1799 was dissolved in 90g of deionized water, heated in a 95℃ water bath, and stirred at 250r / min for 50min to obtain a polymer solution. 33.6g of KOH solid was dissolved in 110g of water to obtain a KOH solution. When the PVA solution turned a pale milky white, the KOH solution was slowly added dropwise to the PVA solution while maintaining heating and stirring for 50min to obtain a PK solution. 500g of cement (PO42.5R) and 150g of fine sand (0.25-0.35mm) were premixed at 70r / min for 10min at 90℃ to obtain a cement-fine sand mixture. The cement-fine sand mixture was added to the PK solution while maintaining 95℃ and stirred at 145r / min for 2min. After this process, the cooler was turned on, and 65g of deionized water at 2℃ was slowly added to lower the slurry temperature to 2℃. Stirring was maintained at 145r / min for 16min to obtain a polymer-cement slurry.

[0092] The positive electrode is prepared as follows: 1.44g Co and 34.8g Ni(OH)₂ are ground for 15 minutes until the powder is dark green. 1.72g of 100-mesh graphite is added (to act as an electron pathway and reduce the interfacial resistance of the particles), and grinding continues for 13 minutes until the powder is grayish-green, obtaining a mixed powder. 17.2g of low-temperature potassium silicate with a modulus of 3.3 is weighed, and 2.8g of deionized water and 1.12g of 100-mesh graphite are added and stirred evenly to obtain a potassium silicate mixture. The mixed powder is added to the potassium silicate mixture in two batches, stirred until a homogeneous slurry is formed, and then evenly coated onto a clean 80mm*80mm square foam nickel substrate (0.32g / cm²). 2 After the electrode film is formed, it is placed under a 320W drying light source for 33 minutes until the electrode surface turns dark green and the center of the area hardens, then sealed and packaged. In this invention, a portion of graphite is pre-dispersed in the adhesive, which reduces the film-forming effect of the adhesive and simultaneously lowers the adhesive's resistance.

[0093] The negative electrode is prepared as follows: 2.4g FeS and 27.2g iron powder are added sequentially to a mortar and ground for 12 minutes until the powder is uniform. Then, 8.4g Fe3O4 is added and grinding continues for 20 minutes until the powder turns dark orange, obtaining a mixed powder. The mixed powder is added in two portions to 18.2g of low-temperature potassium silicate with a modulus of 3.3, and stirred until a homogeneous slurry is formed. This slurry is then uniformly coated onto a clean, square 80mm*80mm nickel foam substrate (0.36g / cm²). 2 Note that the coating method is scraping. After coating the electrode, let it stand for 13 minutes until a film forms on the electrode surface. Then place it under a 320W drying light source for 27 minutes until the center of the electrode area hardens. Seal and bag it.

[0094] Positive and negative electrode sheets were assembled using polymer-cement slurry, placed in a special mold, and cured in a sealed environment at 2°C for 24 hours, followed by standing at room temperature for 24 hours to obtain a cement-based structured battery.

[0095] Example 5: (Polymer solution is PVA-KOH)

[0096] Dissolve 9.5g of PVA1799 in 90g of deionized water, heat in a 95℃ water bath and stir at 250r / min for 50min to obtain a PVA solution; dissolve 30g of KOH solid in 110g of water to obtain a KOH solution; when the PVA solution turns a light milky white color, slowly add the KOH solution dropwise to the PVA solution while maintaining heating and stirring for 50min until the mixed solution turns transparent and light yellow to obtain a PK solution. Premix 490g of cement (PO42.5R) and 140g of fine sand at 70r / min for 10min at 90℃ to obtain a cement-fine sand mixture; while maintaining 90℃, add the cement-fine sand mixture to the PK solution and stir at 145r / min for 2min. After this process, turn on the cooler and slowly add 60g of deionized water at 2℃ to lower the slurry temperature to 2℃, and stir at 145r / min for 16min to obtain a polymer-cement slurry.

[0097] The positive electrode is prepared as follows: 0.36g Co and 8.7g Ni(OH) )2 Grind for 15 minutes until the powder turns dark green. Add 0.43g of 100-mesh graphite and continue grinding for 13 minutes until the powder turns grayish-green, obtaining a mixed powder. Weigh 4.3g of low-temperature potassium silicate with a modulus of 3.3, add 0.7g of deionized water and 0.28g of 100-mesh graphite, and stir until homogeneous to obtain a silicate dispersion. Add the mixed powder to the silicate dispersion in two batches, stirring until a homogeneous slurry is formed. Coat the slurry evenly onto a 2mm*2mm square clean nickel foam substrate (0.35g / cm²). 2After the electrode film is formed, place it under a 320W drying light source for 30 minutes until the electrode surface turns dark green and the center of the area hardens, then seal and bag it.

[0098] The negative electrode is prepared as follows: 0.6g FeS and 6.8g iron powder are ground for 10 minutes until the powder is uniform. 2.1g Fe3O4 is added and grinding continues for 20 minutes until the powder turns dark orange, obtaining a mixed powder. The mixed powder is added in two portions to 4.55g of low-temperature potassium silicate with a modulus of 3.3, and stirred until a homogeneous slurry is formed. This slurry is then uniformly coated onto a 2mm*2mm square clean nickel foam substrate (0.4g / cm²). 2 After coating the electrode, let it stand for 13 minutes until a film forms on the electrode surface. Then, place it under a 320W drying light source for 27 minutes until the center of the electrode area hardens. Finally, seal and bag it.

[0099] The positive and negative electrode sheets were assembled using polymer-cement slurry (that is, the polymer-cement slurry was coated on the surface of the positive and negative electrode sheets respectively), placed in a mold, and cured in a sealed environment at 2°C for 24 hours, and then left to stand at room temperature for 24 hours to obtain a cement-based structured battery.

[0100] Example 6: (Polymer solution is PVA-KOH)

[0101] Dissolve 9.7g of PVA1799 in 90g of deionized water, heat in a 95℃ water bath and stir at 250r / min for 50min to obtain a PVA solution; dissolve 30g of KOH solid in 110g of water to obtain a KOH solution; when the PVA solution turns a light milky white color, slowly add the KOH solution dropwise to the PVA solution while maintaining heating and stirring for 50min until the mixed solution turns transparent and light yellow to obtain a PK solution. Premix 490g of cement (PO42.5R) and 140g of fine sand at 70r / min for 10min at 90℃ to obtain a cement-fine sand mixture; while maintaining 90℃, add the cement-fine sand mixture to the PK solution and stir at 145r / min for 2min. After this process, turn on the cooler and slowly add 60g of deionized water at 2℃ to lower the slurry temperature to 2℃, and stir at 145r / min for 16min to obtain a polymer-cement slurry.

[0102] The positive electrode is prepared as follows: 0.36g Co and 8.7g Ni(OH) )2Grind for 15 minutes until the powder turns dark green. Add 0.43g of 100-mesh graphite and continue grinding for 13 minutes until the powder turns grayish-green, obtaining a mixed powder. Weigh 4.3g of low-temperature potassium silicate with a modulus of 3.3, add 0.7g of deionized water and 0.28g of 100-mesh graphite, and stir until homogeneous to obtain a silicate dispersion. Add the mixed powder to the silicate dispersion in two batches, stirring until a homogeneous slurry is formed. Coat the slurry evenly onto a 2mm*2mm square clean nickel foam substrate (0.35g / cm²). 2 After the electrode film is formed, place it under a 320W drying light source for 30 minutes until the electrode surface turns dark green and the center of the area hardens, then seal and bag it.

[0103] The negative electrode is prepared as follows: 0.6g FeS and 6.8g iron powder are ground for 10 minutes until the powder is uniform. 2.1g Fe3O4 is added and grinding continues for 20 minutes until the powder turns dark orange, obtaining a mixed powder. The mixed powder is added in two portions to 4.55g of low-temperature potassium silicate with a modulus of 3.3, and stirred until a homogeneous slurry is formed. This slurry is then uniformly coated onto a 2mm*2mm square clean nickel foam substrate (0.4g / cm²). 2 After coating the electrode, let it stand for 13 minutes until a film forms on the electrode surface. Then, place it under a 320W drying light source for 27 minutes until the center of the electrode area hardens. Finally, seal and bag it.

[0104] The positive and negative electrode sheets were assembled using polymer-cement slurry (that is, the polymer-cement slurry was coated on the surface of the positive and negative electrode sheets respectively), placed in a mold, and cured in a sealed environment at 2°C for 24 hours, and then left to stand at room temperature for 24 hours to obtain a cement-based structured battery.

[0105] Comparative Example 1: (The polymer solution was PVA-KOH. No cooling process was performed. The mixture was directly stirred and then placed in an environment of 2°C for curing.)

[0106] 10g of PVA1799 was dissolved in 90g of deionized water, heated in a 95℃ water bath, and stirred at 250r / min for 50min to obtain a polymer solution. 33.6g of KOH solid was dissolved in 110g of water to obtain a KOH solution. Once the PVA solution turned a pale milky white, the KOH solution was slowly added dropwise to the PVA solution while maintaining heating and stirring for 50min to obtain a PK solution. 500g of cement (PO42.5R) and 150g of fine sand were premixed at 70r / min for 10min at 90℃ to obtain a cement-fine sand mixture. At room temperature, the cement-fine sand mixture and 65g of room temperature deionized water were added to the PK solution, and the mixture was stirred at 145r / min for 18min to obtain a polymer-cement paste.

[0107] The positive electrode is prepared as follows: 0.36g Co and 8.7g Ni(OH)₂ are ground for 15 minutes until the powder is dark green. 0.43g of 100-mesh graphite is added, and grinding continues for 13 minutes until the powder is grayish-green, obtaining a mixed powder. 4.3g of low-temperature potassium silicate with a modulus of 3.3 is weighed, and 0.7g of deionized water and 0.28g of 100-mesh graphite are added and stirred until homogeneous, obtaining a potassium silicate mixture. The mixed powder is added to the potassium silicate mixture in two batches, stirring until a homogeneous slurry is formed. This slurry is then evenly coated onto a 2mm*2mm square clean nickel foam substrate. After the electrode film is formed, it is placed under a 320W drying light source for 30 minutes until the electrode surface is dark green and the center of the area is hardened. The film is then sealed and packaged.

[0108] The negative electrode is prepared as follows: 0.6g FeS and 6.8g iron powder are ground for 10 minutes until the powder is uniform. 2.1g Fe3O4 is added and grinding continues for 20 minutes to obtain a mixed powder. The mixed powder is added in two batches to 4.55g of low-temperature potassium silicate with a modulus of 3.3, and stirred until a uniform slurry is formed. This slurry is then evenly coated onto a 2mm*2mm square clean nickel foam substrate. After coating, the electrode is allowed to stand for 13 minutes until a film forms on the electrode surface. Then, it is placed under a 320W drying light source for 27 minutes until the center of the electrode area hardens. Finally, it is sealed and packaged.

[0109] Positive and negative electrode sheets were assembled using polymer-cement slurry, placed in a mold, and cured in a sealed environment at 2°C for 24 hours, followed by standing at room temperature for 24 hours to obtain a cement-based structured battery.

[0110] Comparative Example 2: (The polymer solution was PVA-KOH, with a cooling process, and cured at room temperature)

[0111] 10g of PVA1799 was dissolved in 90g of deionized water, heated in a 95℃ water bath, and stirred at 250r / min for 50min to obtain a polymer solution. 33.6g of KOH solid was dissolved in 110g of water to obtain a KOH solution. When the PVA solution turned a pale milky white, the KOH solution was slowly added dropwise to the PVA solution while maintaining heating and stirring for 50min to obtain a PK solution. 500g of cement (PO42.5R) and 150g of fine sand were premixed at 70r / min for 10min at 90℃ to obtain a cement-fine sand mixture. The cement-fine sand mixture was added to the PK solution while maintaining 95℃ and stirred at 145r / min for 2min. After this process, the cooler was turned on, and 65g of deionized water at 2℃ was slowly added to lower the slurry temperature to 2℃. Stirring was maintained at 145r / min for 16min to obtain a polymer-cement slurry.

[0112] The positive electrode is prepared as follows: 0.36g Co and 8.7g Ni(OH)2 are ground for 15 minutes, then 0.43g 100-mesh graphite is added and grinding continues for 13 minutes until the powder turns grayish-green, obtaining a mixed powder. 4.3g of low-temperature potassium silicate with a modulus of 3.3 is weighed, and 0.7g of deionized water and 0.28g of 100-mesh graphite are added and stirred evenly to obtain a potassium silicate mixture. The mixed powder is added to the potassium silicate mixture in two batches, stirring until a homogeneous slurry is formed, and then evenly coated onto a 2mm*2mm square clean nickel foam substrate. After the electrode film is formed, it is placed under a 320W drying light source for 30 minutes until the electrode surface turns dark green and the center of the area hardens, then sealed and packaged.

[0113] The negative electrode was prepared as follows: 0.6g FeS and 6.8g iron powder were ground for 10 minutes, then 2.1g Fe3O4 was added and grinding continued for 20 minutes to obtain a mixed powder. The mixed powder was added in two batches to 4.55g of low-temperature potassium silicate with a modulus of 3.3, and stirred until a homogeneous slurry was formed. This slurry was then uniformly coated onto a 2mm*2mm square clean nickel foam substrate. After coating, the electrode was allowed to stand for 13 minutes until a film formed on the electrode surface. Then, it was placed under a 320W drying light source for 27 minutes until the center of the electrode area hardened. Finally, it was sealed and packaged.

[0114] Positive and negative electrode sheets were assembled using polymer-cement slurry, placed in a mold, and left to stand at room temperature for 48 hours to obtain a cement-based structured battery.

[0115] Comparative Example 3: (Polymer solution was PVA-KOH, no cooling process, cured at room temperature)

[0116] 10g of PVA1799 was dissolved in 90g of deionized water, heated in a 95℃ water bath, and stirred at 250r / min for 50min to obtain a polymer solution. 33.6g of KOH solid was dissolved in 110g of water to obtain a KOH solution. When the PVA solution turned a pale milky white, the KOH solution was slowly added dropwise to the PVA solution while maintaining heating and stirring for 50min to obtain a PK solution. 500g of cement (PO42.5R) and 150g of fine sand were premixed at 70r / min for 10min at 90℃ to obtain a cement-fine sand mixture. The cement-fine sand mixture and 65g of room temperature deionized water were added to the PK solution, and the mixture was stirred at 145r / min for 18min to obtain a polymer-cement paste.

[0117] The positive electrode is prepared as follows: 0.36g Co and 8.7g Ni(OH)₂ are ground for 15 minutes, then 0.43g of 100-mesh graphite is added and grinding continues for 13 minutes to obtain a mixed powder. 4.3g of low-temperature potassium silicate with a modulus of 3.3 is weighed, and 0.7g of deionized water and 0.28g of 100-mesh graphite are added and stirred evenly to obtain a potassium silicate mixture. The mixed powder is added to the potassium silicate mixture in two batches, stirring until a homogeneous slurry is formed. This slurry is then evenly coated onto a 2mm*2mm square clean nickel foam substrate. After the electrode film is formed, it is placed under a 320W drying light source for 30 minutes until the electrode surface turns dark green and the center of the area hardens. The film is then sealed and packaged.

[0118] The negative electrode was prepared as follows: 0.6g FeS and 6.8g iron powder were added sequentially to a mortar and ground for 10 minutes. Then, 2.1g Fe3O4 was added and grinding continued for 20 minutes to obtain a mixed powder. The mixed powder was added in two batches to 4.55g of low-temperature potassium silicate with a modulus of 3.3, and stirred until a homogeneous slurry was formed. This slurry was then evenly coated onto a 2mm*2mm square clean nickel foam substrate. After coating, the electrode was allowed to stand for 13 minutes until a film formed on the electrode surface. Then, it was placed under a 320W drying light source for 27 minutes until the center of the electrode area hardened. Finally, it was sealed and packaged.

[0119] Positive and negative electrode sheets were assembled using polymer-cement slurry, placed in a mold, and left to stand at room temperature for 48 hours to obtain a cement-based structured battery.

[0120] Performance testing:

[0121] Figures 4-9 show the EIS (Nyquist plots) of the batteries prepared in Examples 1-3 and Comparative Examples 1-3, respectively.

[0122] The EIS (Nyquist plot) reflects the ion conductivity of an electrolyte and the electrolyte-electrode interface resistance. The higher the ion conductivity and the lower the electrolyte-electrode interface resistance, the better the performance of the electrolyte.

[0123] The EIS results show that the conductivity of Example 1 is 108 mS / cm, the conductivity of Example 2 is 303 mS / cm, the conductivity of Example 3 is 165.6 mS / cm, the conductivity of Comparative Example 1 is 63.3 mS / cm, the conductivity of Comparative Example 2 is 1.926 mS / cm, and the conductivity of Comparative Example 3 is 0.166 mS / cm.

[0124] As shown in Examples 1-3, the ion conductivity of cement-based structured electrolytes under cooling stirring and low-temperature curing conditions is all above 10. 2 On the order of mS / cm.

[0125] As can be seen from the comparison between Example 1 and Comparative Example 1, the lack of cooling and stirring resulted in a 41.4% decrease in ion conductivity.

[0126] As can be seen from the comparison between Example 1 and Comparative Example 2, the ion conductivity decreased by 98.2% due to the lack of low-temperature curing.

[0127] A comparison of Example 1 and Comparative Example 3 shows that the lack of both cooling and stirring, along with low-temperature curing, resulted in a 99.8% decrease in ion conductivity. This indicates that the product formed by directly mixing the polymer solution with cement does not possess the ability to function as an electrolyte.

[0128] Analysis of the interfacial resistance of Examples 1-3 and Comparative Examples 1-3 shows that the values ​​are mostly around 1 ohm, confirming the enhancing effect of water glass at the electrolyte-electrode interface.

[0129] Figure 10 shows the LSV curves of the batteries prepared in Example 1, Comparative Examples 1 and 3. The longer the LSV window, the more stable the electrolyte. The electrolyte that was cooled, stirred and cured at low temperature (Example 1) was the most stable.

[0130] Figure 11 shows the CV curves of the batteries prepared in Example 1 and Comparative Examples 1 and 3. The CV test method involves applying a linearly changing potential (voltage) and monitoring the corresponding current response. Comparative Example 1 (without cooling and stirring, but with curing at 2-5℃) and Comparative Example 3 (without cooling and stirring, and without curing at 2-5℃) do not exhibit the reaction peaks shown in Example 1. The reaction peaks at 0.74V and 1.00V correspond to the reduction reaction at the iron electrode and the oxidation reaction at the nickel electrode, respectively. Only Example 1 (with electrolyte that has both cooling and constant-rate stirring, and curing at 2-5℃) shows complete reaction peaks, proving the feasibility of applying this electrolyte to all-solid-state alkaline batteries. This demonstrates the superiority of the temperature-controlled, phase-separated cement-based structured electrolyte proposed in this invention in supporting the electroreactions of all-solid-state batteries.

[0131] Figure 12 is the XRD pattern of the positive electrode prepared in Example 1; Figure 13 is the XRD pattern of the negative electrode prepared in Example 1.

[0132] Figure 14 shows the voltage-discharge capacity curves of the batteries prepared in Examples 1-3. Figure 15 shows the voltage-discharge capacity curve of the battery prepared in Example 4. Figure 16 shows the voltage-discharge capacity curves of the batteries prepared in Comparative Examples 1-3.

[0133] In terms of discharge capacity: batteries with cooling and stirring + low-temperature curing (Examples 1-3) can reach a capacity of 50mAh and an areal energy density of 12.5mAh / cm². 2 175Wh / m 2That is, a 6m*6m cement wall can store 6.3kWh of electricity. Keeping the electrolyte constant and increasing the electrode area (Example 4), the capacity can reach 550mAh. Without cooling and stirring (temperature-controlled step 2) (Comparative Example 1), the capacity is only 24mAh; without low-temperature curing (temperature-controlled step 3) (Comparative Example 2), the capacity is only 10mAh; without both (direct mixing of PK and cement, Comparative Example 3), the capacity is only 7mAh. This demonstrates that the temperature-controlled phase separation technology in this invention plays a very important role in the capacity of all-solid-state cement batteries.

[0134] Figure 17 shows the charge-discharge cycle performance test results of the battery prepared in Example 1.

[0135] 2mA / cm was tested specifically for Example 1. 2 The charge-discharge cycle involved 1320s of charging and 1200s of discharging, and the cycle test results were as shown above. The all-solid-state cement-based structure battery of the present invention showed no significant degradation in the first 500 cycles, and after 3000 cycles, the polarization voltage was only 0.3V. The cement battery of the present invention has excellent cycle characteristics and is particularly suitable as a structured energy storage device.

[0136] Figure 18 shows the charge retention performance test curves of Examples 1 and 2 and commercial nickel-iron batteries.

[0137] For Examples 1-2, the battery was charged at a current of 15mA for 3 hours, then left to stand. The open-circuit voltage of the battery was measured every hour and compared with publicly available charge retention data for commercial alkaline nickel-iron batteries. It was found that the voltage retention capability of the cement-based structure battery (unsealed) of the present invention under air conditions is close to that of commercial batteries. Since a primary requirement for energy storage devices is stable charge retention (a significant characteristic distinguishing them from capacitors), the cement-based structure battery of the present invention can certainly be used as an energy storage device.

[0138] Figure 19 shows the LEDs lit by the batteries prepared in Examples 5 and 6 after being connected in series. For Examples 5-6, a red LED was lit after charging at 15mA for 5 minutes.

[0139] The mechanical strengths of the cement-based batteries in Examples 1-3 are shown in Table 1.

[0140] Table 1 Mechanical Strength

[0141] As shown in Table 1, Examples 1-3 have high and stable compressive and flexural strengths and are capable of serving as structures. Therefore, the cement-based battery of the present invention can actually be used as a cement-based structural battery and directly as part of a building (wall, column, slab), participating in load-bearing and serving as an energy storage device to collect clean energy such as solar energy.

[0142] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a cement-based structural battery that integrates load-bearing and energy storage, characterized in that: Including the following steps: 1) The polymer solution, cement, and fine sand are mixed to obtain a polymer-cement paste electrolyte; The polymer solution is obtained by dissolving a polymer and a strong base in water, or by dissolving a polymer, a strong base, and a sulfide in water, or by dissolving a polymer, a strong base, an inorganic sulfide, and a chemical crosslinking agent in water; the polymer is one or more of PVA or PAA; 2) Preparation of the positive electrode sheet; 3) Preparation of the negative electrode sheet; 4) The polymer-cement slurry electrolyte is placed on the surface of the positive electrode and the surface of the negative electrode, respectively. Then the positive electrode and the negative electrode are stacked in sequence, placed in a mold for curing, and left to stand to obtain a cement-based structure battery that integrates load-bearing and energy storage. The mixing described in step 1) specifically involves mixing a solution of polymer and strong alkali, cement and fine sand at 90-95°C, then cooling it to 2-5°C, and simultaneously adding cold water to obtain a cement paste containing a liquid-solid mixed phase.

2. The method for preparing the cement-based structural battery integrating load-bearing and energy storage according to claim 1, characterized in that: When the polymer solution contains inorganic sulfides, the inorganic sulfides are added together with the aforementioned cold water; when the polymer solution contains chemical crosslinking agents, the chemical crosslinking agents are added together with the aforementioned cold water. The amounts of each substance in the polymer solution described in step 1) are, by weight: 8-10 parts of polymer 30-40 parts of strong alkali 190-210 parts water; When inorganic sulfides are present, the amount of sulfide used is 0.5-1 part; When a chemical crosslinking agent is present, the amount of the chemical crosslinking agent used is 0.1-0.5 parts; The amounts of polymer, cement, and fine sand in the polymer solution described in step 1) are as follows by weight: 8-10 parts polymer; 490-510 parts cement; 140-160 parts fine sand. The curing described in step 4) refers to curing in a sealed environment at 0℃~3℃.

3. The method for preparing the cement-based structural battery integrating load-bearing and energy storage according to claim 1, characterized in that: The positive electrode sheet mentioned in step 2) is prepared by the following method: S1: The positive electrode material, conductive agent, binder, and solvent are uniformly mixed to obtain a positive electrode active material slurry; S2: The positive electrode active material slurry is coated on the surface of a conductive substrate, and after film formation, it is dried to obtain a positive electrode sheet; the binder is potassium silicate or sodium silicate.

4. The method for preparing the cement-based structural battery integrating load-bearing and energy storage according to claim 3, characterized in that: The positive electrode material is one or more of nickel hydroxide, transition metals, transition metal oxides, and transition metal hydroxides; the conductive agent is one or more of graphite and carbon nanotubes. The modulus of the water glass is 2.0-3.3; the solvent is water. The mass ratio of the positive electrode material, conductive agent and binder is (8-9.5):(0.5-1):(3-6).

5. The method for preparing the cement-based structural battery integrating load-bearing and energy storage according to claim 3, characterized in that: The mass ratio of the positive electrode material to the solvent is (8-9.5):(0.4-0.8); The coating amount of the positive electrode active material slurry is 0.3-0.4 g / cm³. 2 ; The positive electrode active material slurry is coated on both surfaces of the conductive substrate; The conductive agent is divided into two parts: one part is mixed with the positive electrode material, and the other part is mixed with the binder and solvent. The conductive substrate is nickel foam, copper foil, or aluminum foil.

6. The method for preparing the cement-based structural battery integrating load-bearing and energy storage according to claim 1, characterized in that: The negative electrode sheet described in step 3) is prepared by the following method: the negative electrode active material, conductive agent and binder are uniformly mixed to obtain a negative electrode active material slurry; the negative electrode active material slurry is coated on the surface of a conductive substrate, and after film formation, it is dried to obtain a negative electrode sheet; the binder is one or more of potassium silicate and sodium silicate.

7. The method for preparing the cement-based structural battery integrating load-bearing and energy storage according to claim 6, characterized in that: The negative electrode active material is one or more of the following: iron, iron oxide, iron(II,III) oxide, iron carbonyl, ferrous sulfide, bismuth sulfide, zinc, zinc oxide, zinc-containing alloys, and iron-containing alloys. The conductive agent is one or more of carbon nanotubes and graphite; The coating amount of the negative electrode active material slurry is 0.35-0.45 g / cm³. 2 ; The mass ratio of the negative electrode active material, conductive agent, and binder is (7.5-10):(0-0.5):(3-5.5); The conductive substrate is nickel foam, copper foil, or aluminum foil.

8. The method for preparing the cement-based structural battery integrating load-bearing and energy storage according to claim 1, characterized in that: The cement paste containing the liquid-solid mixed phase is prepared under stirring conditions, with a stirring speed of 135-165 r / min. The mixing time at 90-95℃ in step 1) is 1-2 minutes; the cooling to 2-5℃ means cooling to 2-5℃ in 5-10 minutes; after adding cold water and cooling to 2-5℃, stir and mix for 15-20 minutes. Step 1) describes mixing the polymer and strong alkali solution, cement, and fine sand at 90-95℃. This refers to stirring the polymer, strong alkali, and water at 85-95℃ at a speed of 250-260 r / min for 1.5-2 hours to prepare a solution; dry mixing the cement and fine sand at 90-95℃ at a speed of 60-70 r / min for 5-10 minutes to obtain a cement-fine sand mixture; and then mixing the above solution and cement-fine sand mixture at 90-95℃. The mass ratio of cold water to polymer is (60-80):(8-10).

9. The method for preparing the cement-based structural battery integrating load-bearing and energy storage according to claim 1, characterized in that: The strong base mentioned in step 1) is one or more of KOH and NaOH; the sulfide is one or more of Na2S or K2S; and the chemical crosslinking agent is one or more of tetraethylammonium chloride and polyethylene glycol diglycidyl ether. The polymer PVA has a molecular weight of 1000-10000, and the PAA has a molecular weight of 10000-500000. The curing mentioned in step 4) refers to curing in a sealed environment at 0℃~3℃ for 6-24 hours; the static setting mentioned in step 4) refers to setting at room temperature for 12h~24h.

10. A cement-based structural battery integrating load-bearing and energy storage, prepared by the method according to any one of claims 1 to 9.

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