Intrinsic tensile polymer rechargeable cement-based battery and preparation method thereof

Abstract

The invention discloses an intrinsic tensile polymer rechargeable cement-based battery and a preparation method thereof. The cement-based battery comprises a positive electrode, a positive electrode electrolyte bonding layer, an electrolyte, a negative electrode electrolyte bonding layer, a negative electrode and a metal conductive material which are sequentially arranged, the metal conductive material comprises a positive electrode current collector and a negative electrode current collector, half of the positive electrode current collector and half of the negative electrode current collector are embedded into the positive electrode and the negative electrode respectively, and raw materials of the electrolyte are cement and water. The raw materials of the positive electrode are manganese dioxide, cement, water, a water reducing agent and carbon black, the raw materials of the negative electrode are cement, zinc powder, water, a water reducing agent and carbon black, the raw materials of the positive electrode electrolyte bonding layer are polyvinylidene fluoride, and the raw materials of the negative electrode electrolyte bonding layer are butadiene styrene rubber and water. According to the invention, common cement materials are used for preparing the rechargeable cement-based battery with the tensile property, so that the rechargeable cement-based battery is easy to manufacture and low in cost, has excellent conductivity and tensile property, conforms to the awareness of green and low carbon, and can lay a foundation for green and intelligent development of existing building materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of new building materials, and in particular relates to an intrinsic stretchable polymer rechargeable cement-based battery and a preparation method thereof. Background Art

[0002] Cement concrete is one of the most widely used building materials. The building materials industry has a huge demand for cement concrete, and the market demand for batteries is also huge. The organic combination of the two will have huge application prospects.

[0003] With the large-scale application of renewable energy, efficient and safe energy storage technologies have become key to addressing energy volatility. While traditional batteries offer high energy density, they suffer from issues such as flammable electrolytes, high costs, poor stretchability, and difficulty integrating with building structures, limiting their application in large-scale energy storage scenarios. As an emerging form of energy storage, rechargeable cement-based batteries with stretchable properties demonstrate unique potential by leveraging the ionic conductivity of cement materials and their advantages of building integration. However, existing technologies still face multiple challenges. Summary of the Invention

[0004] The purpose of the present invention is to provide an intrinsically stretchable polymer rechargeable cement-based battery and a preparation method thereof, which solves the problem that clean energy generation is highly random and intermittent, the generated electricity requires large-scale energy storage management, and traditional battery electrolytes are flammable, costly, and have poor electrolyte stretching properties, which affect their energy storage efficiency.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is: An intrinsic stretchable polymer rechargeable cement-based battery, comprising a positive electrode, an electrolyte, a negative electrode, and a metal conductive material arranged in sequence, wherein the metal conductive material comprises a positive electrode current collector and a negative electrode current collector, half of the positive electrode current collector is embedded in the positive electrode, and half of the negative electrode current collector is embedded in the negative electrode, a positive electrode electrolyte bonding layer is provided between the electrolyte and the positive electrode, and a negative electrode electrolyte bonding layer is provided between the electrolyte and the negative electrode; The electrolyte is composed of the following raw materials in percentage by weight: cement 65% to 85%, water 15% to 35%; The positive electrode is composed of the following raw materials in percentage by weight: manganese dioxide 60% to 65%, cement 20% to 25%, water 5% to 10%, water reducer 3% to 3.5%, and carbon black 4% to 8%; The negative electrode is composed of the following raw materials in percentage by weight: cement 60% to 65%, zinc powder 15% to 20%, water 15% to 20%, water reducer 0.9% to 1.2%, and carbon black 1.5% to 3%; The positive electrode electrolyte bonding layer is composed of the following raw materials in percentage by weight: polyvinylidene fluoride (RVDF) 10% to 20%, water 80% to 90%; The negative electrode electrolyte bonding layer is composed of the following raw materials in percentage by mass: 10% to 20% styrene-butadiene rubber (SBR) and 80% to 90% water.

[0006] Compared to existing technologies, this invention uses common cement materials as its primary component, not only reducing battery production costs but also ensuring good compatibility between the battery and building materials, providing new insights into the green and intelligent development of building materials. By optimizing the electrolyte composition and electrode design, this invention improves the ionic conductivity, electrode stability, and electrical performance of cement-based batteries, thereby enhancing the battery's output current, energy density, and cycle life.

[0007] Furthermore, the cement is ordinary Portland cement, in which the mass percentage content of dicalcium silicate is 45% to 60%, the mass percentage content of tricalcium silicate is 15% to 30%, the mass percentage content of tricalcium aluminate is 5% to 12%, and the mass percentage content of tetracalcium aluminoferrite is 6% to 8%.

[0008] Furthermore, the water reducer is a polycarboxylic acid water reducer with a water reduction rate of 20% to 30% and a solid content of 10% to 20%.

[0009] Furthermore, the manganese dioxide used as the main active material of the positive electrode has a purity of ≥91%, heavy metal impurities Fe≤0.03%, Cu≤0.005%, a particle size of 10-50㎛, and a gram capacity of manganese dioxide of 300mAh / g~320mAh / g.

[0010] Furthermore, the carbon black is a conductive material with a particle size of 30-50 nm and a gram capacity of 25 mAh / g to 55 mAh / g.

[0011] Furthermore, the particle size of the main active material zinc powder in the negative electrode is 1-100 nm, and the gram capacity of the zinc powder is 400 mAh / g to 600 mAh / g.

[0012] Furthermore, the zinc powder needs to be cleaned with acetic acid to remove the oxide layer, and then washed with ethanol to remove the residual acetic acid and then dried.

[0013] Furthermore, the positive electrode current collector is an aluminum sheet, the negative electrode current collector is a copper sheet, and half of the positive and negative current collectors are respectively embedded in the positive and negative poles of the cement-based battery. Metal anti-rust paper is used during maintenance to adhere to the metal surface.

[0014] Furthermore, the molar mass of the polyvinylidene fluoride is 3.0×10 5g / mol ~6.0×10 5 g / mol.

[0015] Furthermore, the molar mass of the styrene-butadiene rubber is 0.5×10 5 g / mol ~3.0×10 5 g / mol.

[0016] This invention not only solves the application challenges of traditional batteries in large-scale energy storage scenarios, but also demonstrates unique advantages in integration with building structures. This is achieved by using ordinary Portland cement as the primary component, combining optimized electrolyte composition and electrode design, improving material tensile properties, and introducing metallic conductive materials and a specialized electrolyte bonding layer.

[0017] The present invention also provides a method for preparing an intrinsically stretched polymer rechargeable cement-based battery, comprising the following steps: S1. Weigh the raw materials according to the above-mentioned design ratio to prepare electrolyte slurry, positive electrode slurry, negative electrode slurry, positive electrode electrolyte bonding layer slurry, and negative electrode electrolyte bonding layer slurry respectively; S2. Add the electrolyte slurry, positive electrode slurry, and negative electrode slurry into the mold respectively, embed half of the positive electrode current collector and half of the negative electrode current collector into the positive electrode slurry and negative electrode slurry respectively, and cure and dry to obtain the electrolyte block, positive electrode block, and negative electrode block; S3. Use the positive electrode electrolyte bonding layer slurry to bond one side of the electrolyte block to the positive electrode block, and use the negative electrode electrolyte bonding layer slurry to bond the other side of the electrolyte block to the negative electrode block, and then solidify to obtain a rechargeable cement-based battery with tensile properties.

[0018] This invention successfully improves the ionic conductivity, electrode stability, and electrical conductivity of cement-based batteries while maintaining good structural strength. The stretchable rechargeable cement-based battery produced by this invention demonstrates excellent performance in terms of electrical energy stretch regulation, energy storage density, cycle life, and engineering applicability, providing new solutions and possibilities for the green and intelligent development of building materials.

[0019] The present invention solves the problems of existing battery electrolytes, such as high cost, unsafety, and poor tensile properties of the electrolyte, which lead to the inability to improve the energy storage efficiency and ensure the battery strength at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a schematic diagram of the structure of a rechargeable cement-based battery with stretchable properties according to the present invention; wherein: 1. electrolyte; 2. positive electrode; 3. negative electrode; 4. positive electrode current collector; 5. negative electrode current collector; 6. positive electrode electrolyte bonding layer; 7. negative electrode electrolyte bonding layer. DETAILED DESCRIPTION

[0021] The present invention is further described in detail below with reference to the examples.

[0022] The present invention addresses the problems of existing cement-based batteries, such as low electrical conductivity, high interface resistance, easy electrode passivation, and insufficient mechanical properties. By optimizing the material ratio, introducing an electrolyte bonding layer, and improving the electrode and electrolyte interface design, the product is given stretchable properties, achieving a synergistic improvement in electrochemical performance and structural strength.

[0023] The physicochemical indicators of the raw materials used in the following examples are as follows: Cement: Ordinary Portland cement, wherein the mass percentage content of dicalcium silicate is 45% to 60%, the mass percentage content of tricalcium silicate is 15% to 30%, the mass percentage content of tricalcium aluminate is 5% to 12%, and the mass percentage content of tetracalcium aluminoferrite is 6% to 8%.

[0024] Water reducer: polycarboxylate water reducer, water reduction rate is 25%, solid content is 15%.

[0025] The main active material of the positive electrode is manganese dioxide: the particle size is 30㎛, and the gram capacity of manganese dioxide is 310mAh / g.

[0026] Carbon black: particle size is 40nm, and carbon black gram capacity is 40mAh / g.

[0027] The main active material for the negative electrode, zinc powder, has a particle size of 50nm and a gram capacity of 500mAh / g. The zinc powder needs to be cleaned with acetic acid to remove the oxide layer, then rinsed with ethanol to remove any remaining acetic acid, and then dried.

[0028] Metal conductive materials: The positive electrode current collector is aluminum sheet, the negative electrode current collector is copper sheet, and the anti-rust paper used for maintenance is M3 anti-rust paper.

[0029] Polyvinylidene fluoride: molar mass is 4.5×10 5 g / mol.

[0030] Styrene butadiene rubber: molar mass is 2.0×10 5 g / mol. Example 1

[0031] An intrinsic stretchable polymer rechargeable cement-based battery comprises a positive electrode, an electrolyte, a negative electrode and a metal conductive material arranged in sequence, wherein the metal conductive material comprises a positive electrode current collector and a negative electrode current collector, half of the positive electrode current collector is embedded in the positive electrode, and half of the negative electrode current collector is embedded in the negative electrode, a positive electrode electrolyte bonding layer is provided between the electrolyte and the positive electrode, and a negative electrode electrolyte bonding layer is provided between the electrolyte and the negative electrode.

[0032] The electrolyte is composed of raw materials in the following mass percentages: cement 65%, water 35%.

[0033] The positive electrode is composed of the following raw materials in the following mass percentages: manganese dioxide 60%, cement 20%, water 10%, water reducer 3%, and carbon black 7%.

[0034] The negative electrode is composed of the following raw material components by mass percentage: cement 60%, zinc powder 15.8%, water 20%, water reducer 1.2%, and carbon black 3%.

[0035] Metal conductive material: The positive electrode current collector is aluminum sheet, and the negative electrode current collector is copper sheet.

[0036] The positive electrode electrolyte bonding layer is composed of the following raw materials in the following mass percentages: polyvinylidene fluoride (RVDF) 10%, water 90%.

[0037] The negative electrode electrolyte bonding layer is composed of the following raw materials in the following mass percentages: 10% styrene-butadiene rubber (SBR) and 90% water.

[0038] The method for preparing a rechargeable cement-based battery comprises the following steps: S1. Put cement and water into a cement slurry mixer and stir at a speed of 62 r / min for 5 min to obtain an electrolyte slurry; Manganese dioxide, cement, and carbon black were placed in a cement slurry mixer and dry-mixed at a speed of 62 r / min for 2 min. Water and polycarboxylate water reducer were then added and stirred at a speed of 62 r / min for 5 min to obtain a positive electrode slurry. Zinc powder, cement, and carbon black were placed in a cement slurry mixer and dry-mixed at a speed of 62 r / min for 2 min. Water and polycarboxylate water reducer were then added and stirred at a speed of 62 r / min for 5 min to obtain a negative electrode slurry. Add polyvinylidene fluoride into a cement slurry mixer, add water, and stir at a speed of 62 r / min for 5 minutes to obtain a positive electrode electrolyte bonding layer slurry; Add styrene-butadiene rubber into a cement slurry mixer, add water, and stir at a speed of 62 r / min for 5 minutes to obtain a negative electrode electrolyte bonding layer slurry; S2. Pour the electrolyte slurry into a 10cm×10cm×3cm mold, pour the positive electrode slurry and the negative electrode slurry into a 10cm×10cm×5cm mold respectively, and embed half of the positive electrode current collector aluminum sheet and the negative electrode current collector copper sheet into the positive electrode slurry and the negative electrode slurry respectively; After standing for one day, the electrolyte slurry, positive electrode slurry, and negative electrode slurry solidify into a block. Then, remove the mold, affix anti-rust paper to the exposed positive electrode current collector and negative electrode current collector, and place the block in a curing box (temperature 20±2℃, humidity>95%) for standard curing for 28 days. S4. Place the cured electrolyte block, positive electrode block, and negative electrode block into a vacuum drying oven at 60°C and dry the blocks to constant weight. S5. Use the positive electrode electrolyte bonding layer slurry to bond one side of the electrolyte block to the positive electrode block, and use the negative electrode electrolyte bonding layer slurry to bond the other side of the electrolyte block to the negative electrode block. Let it stand for 5 hours to allow the bonding layer material to solidify, and obtain a rechargeable cement-based battery with tensile properties. Example 2

[0039] An intrinsic stretchable polymer rechargeable cement-based battery comprises a positive electrode, an electrolyte, a negative electrode and a metal conductive material arranged in sequence, wherein the metal conductive material comprises a positive electrode current collector and a negative electrode current collector, half of the positive electrode current collector is embedded in the positive electrode, and half of the negative electrode current collector is embedded in the negative electrode, a positive electrode electrolyte bonding layer is provided between the electrolyte and the positive electrode, and a negative electrode electrolyte bonding layer is provided between the electrolyte and the negative electrode.

[0040] The electrolyte is composed of raw materials in the following mass percentages: cement 70%, water 30%.

[0041] The positive electrode is composed of the following raw materials in percentage by mass: manganese dioxide 60%, cement 25%, water 5.5%, water reducer 3.5%, and carbon black 6%.

[0042] The negative electrode is composed of the following raw materials in percentage by mass: cement 60%, zinc powder 20%, water 15.8%, water reducer 1.2%, and carbon black 3%.

[0043] Metal conductive material: The positive electrode current collector is aluminum sheet, and the negative electrode current collector is copper sheet.

[0044] The positive electrode electrolyte bonding layer is composed of the following raw materials in the following mass percentages: polyvinylidene fluoride (RVDF) 15%, water 85%.

[0045] The negative electrode electrolyte bonding layer is composed of the following raw materials in the following mass percentages: 15% styrene-butadiene rubber (SBR) and 85% water.

[0046] The preparation method of the rechargeable cement-based battery is the same as that in Example 1. Example 3

[0047] An intrinsic stretchable polymer rechargeable cement-based battery comprises a positive electrode, an electrolyte, a negative electrode and a metal conductive material arranged in sequence, wherein the metal conductive material comprises a positive electrode current collector and a negative electrode current collector, half of the positive electrode current collector is embedded in the positive electrode, and half of the negative electrode current collector is embedded in the negative electrode, a positive electrode electrolyte bonding layer is provided between the electrolyte and the positive electrode, and a negative electrode electrolyte bonding layer is provided between the electrolyte and the negative electrode.

[0048] The electrolyte is composed of raw materials in the following mass percentages: cement 75%, water 25%.

[0049] The positive electrode is composed of the following raw materials in percentage by mass: manganese dioxide 65%, cement 20%, water 5%, water reducer 3.5%, and carbon black 6.5%.

[0050] The negative electrode is composed of the following raw materials in percentage by weight: cement 65%, zinc powder 15.8%, water 15%, water reducer 1.2%, and carbon black 3%.

[0051] Metal conductive material: The positive electrode current collector is aluminum sheet, and the negative electrode current collector is copper sheet.

[0052] The positive electrode electrolyte bonding layer is composed of the following raw materials in the following mass percentages: polyvinylidene fluoride (RVDF) 20% and water 80%.

[0053] The negative electrode electrolyte bonding layer is composed of the following raw materials in the following mass percentages: styrene-butadiene rubber (SBR) 20% and water 80%.

[0054] The preparation method of the rechargeable cement-based battery is the same as that in Example 1. Example 4

[0055] An intrinsic stretchable polymer rechargeable cement-based battery comprises a positive electrode, an electrolyte, a negative electrode and a metal conductive material arranged in sequence, wherein the metal conductive material comprises a positive electrode current collector and a negative electrode current collector, half of the positive electrode current collector is embedded in the positive electrode, and half of the negative electrode current collector is embedded in the negative electrode, a positive electrode electrolyte bonding layer is provided between the electrolyte and the positive electrode, and a negative electrode electrolyte bonding layer is provided between the electrolyte and the negative electrode.

[0056] The electrolyte is composed of the following raw materials in the following mass percentages: cement 85%, water 15%.

[0057] The positive electrode is composed of the following raw materials in percentage by weight: manganese dioxide 63.5%, cement 20%, water 5%, water reducer 3.5%, and carbon black 8%.

[0058] The negative electrode is composed of the following raw materials in percentage by weight: cement 60.8%, zinc powder 20%, water 15%, water reducer 1.2%, and carbon black 3%.

[0059] Metal conductive material: The positive electrode current collector is aluminum sheet, and the negative electrode current collector is copper sheet.

[0060] The positive electrode electrolyte bonding layer is composed of the following raw materials in the following mass percentages: polyvinylidene fluoride (RVDF) 17%, water 83%.

[0061] The negative electrode electrolyte bonding layer is composed of the following raw materials in percentage by weight: 17% styrene-butadiene rubber (SBR) and 83% water.

[0062] The preparation method of the rechargeable cement-based battery is the same as that in Example 1.

[0063] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Modifications and changes may be made to the above embodiments without departing from the spirit and scope of the present invention.

Claims

1. An intrinsic stretchable polymer rechargeable cement-based battery, characterized in that: It includes a positive electrode, an electrolyte, a negative electrode and a metal conductive material arranged in sequence, wherein the metal conductive material includes a positive electrode current collector and a negative electrode current collector, half of the positive electrode current collector is embedded in the positive electrode, and half of the negative electrode current collector is embedded in the negative electrode, a positive electrode electrolyte bonding layer is provided between the electrolyte and the positive electrode, and a negative electrode electrolyte bonding layer is provided between the electrolyte and the negative electrode; The electrolyte is composed of the following raw materials in percentage by weight: cement 65% to 85%, water 15% to 35%; The positive electrode is composed of the following raw materials in percentage by weight: manganese dioxide 60% to 65%, cement 20% to 25%, water 5% to 10%, water reducer 3% to 3.5%, and carbon black 4% to 8%; The negative electrode is composed of the following raw materials in percentage by weight: cement 60% to 65%, zinc powder 15% to 20%, water 15% to 20%, water reducer 0.9% to 1.2%, and carbon black 1.5% to 3%; The positive electrode electrolyte bonding layer is composed of the following raw materials in percentage by weight: 10% to 20% polyvinylidene fluoride and 80% to 90% water; The negative electrode electrolyte bonding layer is composed of the following raw materials in percentage by mass: 10% to 20% styrene-butadiene rubber and 80% to 90% water.

2. The intrinsic stretchable polymer rechargeable cement-based battery according to claim 1, characterized in that: The cement is ordinary Portland cement.

3. The intrinsic stretchable polymer rechargeable cement-based battery according to claim 1, characterized in that: The water reducer is a polycarboxylic acid water reducer with a water reduction rate of 20% to 30% and a solid content of 10% to 20%.

4. The intrinsic stretchable polymer rechargeable cement-based battery according to claim 1, characterized in that: The manganese dioxide in the positive electrode raw material has a purity of ≥91%, heavy metal impurities Fe≤0.03%, Cu≤0.005%, a particle size of 10-50㎛, and a gram capacity of manganese dioxide of 300mAh / g~320mAh / g.

5. The intrinsic stretchable polymer rechargeable cement-based battery according to claim 1, characterized in that: The carbon black particle size is 30-50 nm, and the carbon black gram capacity is 25 mAh / g-55 mAh / g.

6. The intrinsic stretchable polymer rechargeable cement-based battery according to claim 1, characterized in that: The particle size of the zinc powder is 1-100 nm, and the gram capacity of the zinc powder is 400 mAh / g to 600 mAh / g.

7. The intrinsic stretchable polymer rechargeable cement-based battery according to claim 1, characterized in that: The positive electrode current collector is an aluminum sheet, and the negative electrode current collector is a copper sheet.

8. The intrinsic stretchable polymer rechargeable cement-based battery according to claim 1, characterized in that: The molar mass of the polyvinylidene fluoride is 3.0×10 5 g / mol ~6.0×10 5 g / mol, the molar mass of the styrene-butadiene rubber is 0.5×10 5 g / mol ~3.0×10 5 g / mol.

9. The method for preparing an intrinsic stretched polymer rechargeable cement-based battery according to any one of claims 1 to 8, characterized in that: The steps include: S1. Weigh the raw materials according to the designed ratio to prepare electrolyte slurry, positive electrode slurry, negative electrode slurry, positive electrode electrolyte bonding layer slurry, and negative electrode electrolyte bonding layer slurry respectively; S2. Add the electrolyte slurry, positive electrode slurry, and negative electrode slurry into the mold respectively, embed half of the positive electrode current collector and half of the negative electrode current collector into the positive electrode slurry and negative electrode slurry respectively, remove the mold after coagulation, and perform curing and drying to obtain the electrolyte block, positive electrode block, and negative electrode block; S3. Use the positive electrode electrolyte bonding layer slurry to bond one side of the electrolyte block to the positive electrode block, and use the negative electrode electrolyte bonding layer slurry to bond the other side of the electrolyte block to the negative electrode block, and then solidify to obtain a rechargeable cement-based battery with tensile properties.

10. The method for preparing an intrinsically stretched polymer rechargeable cement-based battery according to claim 9, characterized in that: In step S1, the zinc powder in the negative electrode material is first washed with acetic acid to remove the oxide layer, and then the residual acetic acid is washed with ethanol, and then dried to prepare the negative electrode slurry; In step S2, half of the positive electrode current collector and half of the negative electrode current collector are embedded in the positive electrode slurry and the negative electrode slurry respectively. After solidification, the mold is removed, and the exposed positive electrode current collector and negative electrode current collector are covered with anti-rust paper and then cured.

Images