Carbon mineralization structure supercapacitor and preparation method and application thereof

Abstract

The invention provides a carbon mineralization structure supercapacitor and a preparation method and application thereof. The supercapacitor with the carbon mineralization structure comprises an electrode, the electrode comprises a carbon mineralization gel material, a carbon conductive material and foam metal, and the carbon conductive material is distributed in a three-dimensional space formed after the carbon mineralization gel material is carbonized and wraps the foam metal together; the electrodes are arranged on the two sides of the solid electrolyte layer, and the preparation raw materials of the solid electrolyte layer comprise a carbon mineralization cementing material, bicarbonate, a fiber material, a porous micro-nano material, an air entraining agent and an inorganic salt aqueous solution, raw materials for preparing the solid electrolyte layer are mixed, pressed and carbonized to form the solid electrolyte layer. The carbon mineralization structure supercapacitor provided by the invention breaks through the bottlenecks of low strength and poor energy storage performance of a traditional cement-based capacitor, has excellent mechanical properties and electrical properties at the same time, and is low in cost and environment-friendly.

Description

Technical Field

[0001] The present invention relates to the technical field of structure-energy storage integrated materials, and particularly relates to a carbonated structure supercapacitor, a preparation method thereof, and an application thereof. Background Art

[0002] In recent years, with the intensification of energy consumption and environmental pollution problems, new energies such as solar energy and wind energy have attracted much attention. However, the problem of energy supply-demand mismatch caused by their intermittency and volatility needs to be solved urgently. Therefore, composite materials and structures with both energy storage and structural functions have become a research hotspot. They can reduce the self-weight and volume of energy storage devices, lower system complexity, failure rate, and cost, and particularly show great application value in fields such as aerospace, automobiles, and buildings. Among them, structural supercapacitors have attracted much attention due to their high energy density, high power density, and durability.

[0003] However, there is a contradiction between the electrical properties and mechanical properties of structural supercapacitors, that is, improving mechanical properties often comes at the expense of electrical properties, and vice versa. Although various solutions have been proposed, this contradiction has not been completely resolved. Especially in the construction field, with the continuous increase of global carbon emissions, it is urgent to reduce energy consumption and carbon emissions in the construction industry. Developing building materials into large-scale electrochemical energy storage devices to achieve self-power supply and green sustainable development of buildings has become an effective way to solve the energy supply-demand mismatch and reduce carbon emissions.

[0004] Cement-based materials are the main matrix materials of building components, but there are still many challenges as structural supercapacitors. For example, cement-based solid electrolytes have problems such as difficult-to-control porosity, low ionic conductivity, and difficulty in balancing mechanical properties and electrochemical properties. At the same time, the cumbersome preparation, high price, or insufficient performance of electrode materials also limit the application of structural supercapacitors. More seriously, the electrode passivation effect caused by the alkaline environment (pH>12) of cement electrolytes may increase the interfacial charge transfer impedance by 2-3 orders of magnitude, which will also greatly limit the energy storage performance of cement capacitors. Taking the invention patent CN107195478A as an example, it introduces a graphene / magnesium phosphate cement structural supercapacitor, using graphene as the electrode and magnesium phosphate cement (containing heavy magnesium oxide, potassium dihydrogen phosphate, borax, and fly ash) as the solid electrolyte. The preparation of this capacitor is relatively simple, and the early compressive strength of the solid electrolyte can reach 5-7.5 MPa. However, this technology still has limitations, such as poor workability of magnesium phosphate cement, insufficient later strength to meet the building load-bearing requirements, and high cost of potassium dihydrogen phosphate. More critically, the liquid-phase ion concentration in this system is limited (<1 mol / L), resulting in a volume energy density of less than 15 Wh / L, only 1 / 20 of the lithium battery system. These factors limit its large-scale application in the construction field. Summary of the Invention

[0005] The present invention aims to solve at least one of the technical problems in the prior art to a certain extent. To this end, an object of the present invention is to provide a carbon mineralized structure supercapacitor, a preparation method thereof, and an application thereof.

[0006] In a first aspect of the present invention, the present invention provides a carbon mineralized structure supercapacitor, which includes: An electrode, the electrode includes a carbon mineralized cementitious material, a carbon conductive material, and a foam metal, and the carbon conductive material is distributed in a three-dimensional space formed after the carbon mineralized cementitious material is carbonized and jointly coats the foam metal; A solid electrolyte layer, the electrodes are arranged on both sides of the solid electrolyte layer, and the preparation raw materials of the solid electrolyte layer include: a carbon mineralized cementitious material, a bicarbonate, a fibrous material, a porous micro-nano material, an air-entraining agent, and an inorganic salt aqueous solution. The preparation raw materials of the solid electrolyte layer are mixed, pressed, and carbonized to form a solid electrolyte layer.

[0007] According to the above carbon mineralized structure supercapacitor provided by the present invention, on the one hand, the carbon mineralized cementitious material is mainly composed of calcium carbonate and silica gel, and has high strength characteristics. In the preparation of the electrode, by introducing a carbon conductive material into the three-dimensional space in the carbon mineralized cementitious material, and the carbon mineralized cementitious material and the carbon conductive material as a whole coat the foam metal, a structural electrode with both high strength and a continuous conductive network can be formed. On the other hand, in the preparation raw materials of the solid electrolyte layer, the carbon mineralized cementitious material can be carbonized to form a high-strength carbonized matrix, and by adding a bicarbonate, a porous micro-nano material, a fibrous material, and an air-entraining agent, it helps to form a uniform pore structure and an efficient ion transport channel in the above carbonized matrix, thereby greatly improving the ion conductivity of the structural electrolyte. At the same time, in view of the specific structure and composition of the carbonized matrix, an inorganic salt ion solution is selected as the electrolyte, which can not only better maintain the structural stability of the carbon mineralized matrix, but also effectively reduce the corrosion of the electrode. In addition, since both the electrode and the solid electrolyte layer use the carbon mineralized cementitious material as the core, after forming a sandwich laminate structure by pressing, the carbonization effect can further enhance the close contact between the electrode and the electrolyte layer, thereby improving the charge and discharge performance of the carbon mineralized structure supercapacitor.

[0008] In some embodiments of the present invention, the mass ratio of the carbon mineralized cementitious material to the carbon conductive material is 100:(0.5 - 10).

[0009] In some embodiments of the present invention, the carbon conductive material is selected from at least one of carbon black, carbon nanotubes, carbon fibers, and graphene.

[0010] Preferably, the particle sizes of carbon black and graphene are ≤50 nm, and the lengths of carbon nanotubes or carbon fibers are 7 - 15 μm, and the diameters are 5 - 15 nm.

[0011] In some embodiments of the present invention, the thickness of the metallic foam is 1 mm - 2 mm; preferably, the metallic foam is selected from nickel foam, iron foam or copper foam.

[0012] In some embodiments of the present invention, the thickness of the electrode is 2 mm - 5 mm.

[0013] In some embodiments of the present invention, the carbonated cementitious material contains β-C2S, γ-C2S, C3S2 and CS. Preferably, the total content of β-C2S and C3S2 is not less than 70 wt%, and the residue on 80 μm sieve is < 1%. Those skilled in the art can understand that the carbonated cementitious material may also include industrial solid wastes and their by-products containing the above-mentioned β-C2S, γ-C2S, C3S2 and CS.

[0014] In some embodiments of the present invention, the thickness of the solid electrolyte layer is 3 mm - 20 mm.

[0015] In some embodiments of the present invention, the bicarbonate is selected from at least one of NaHCO3, KHCO3 and NH4HCO3.

[0016] In some embodiments of the present invention, the fibrous material is selected from at least one of polypropylene fiber and glass fiber. Preferably, the fiber diameter of the fibrous material is less than 30 μm and the length is less than 1 mm.

[0017] In some embodiments of the present invention, the porous micro-nano material is selected from at least one of porous calcium carbonate and porous silica.

[0018] In some embodiments of the present invention, the air-entraining agent is selected from at least one of alkyl benzene sulfonate compounds and rosin resin compounds.

[0019] Furthermore, the alkyl benzene sulfonate compounds include sodium alkyl benzene sulfonate, sodium alkyl sulfonate, etc.; the rosin resin compounds include rosin thermopolymer, rosin soap, etc.

[0020] In some embodiments of the present invention, the inorganic salt in the inorganic salt aqueous solution is selected from at least one of NaCl, Na2SO4 and KCl. Preferably, it is a neutral inorganic salt aqueous solution. More preferably, the concentration of the inorganic salt aqueous solution is 1 mol / L - 2 mol / L. The neutral inorganic salt ion solution as the electrolyte can not only better maintain the structural stability of the carbonated matrix, but also effectively reduce the corrosion of the electrode.

[0021] In some embodiments of the present invention, the mass of the bicarbonate is 1 - 5% of the carbonated cementitious material, preferably 2 - 4%.

[0022] In some embodiments of the present invention, the mass of the fibrous material is 1-15% of the carbon mineralized cementitious material, preferably 2-10%.

[0023] In some embodiments of the present invention, the mass of the porous micro-nano material is 0.5-5% of the carbon mineralized cementitious material, preferably 1-5%.

[0024] In some embodiments of the present invention, the mass of the air-entraining agent is 0.005-0.05% of the carbon mineralized cementitious material, preferably 0.025-0.04%.

[0025] In some embodiments of the present invention, the mass of the bicarbonate is 1-5% of the carbon mineralized cementitious material, the mass of the fibrous material is 1-15% of the carbon mineralized cementitious material, the mass of the porous micro-nano material is 0.5-5% of the carbon mineralized cementitious material, and the mass of the air-entraining agent is 0.005-0.05% of the carbon mineralized cementitious material. Controlling the bicarbonate, fibrous material, porous micro-nano material, and air-entraining agent within the above ranges can form a uniform and rich pore structure in the carbonized matrix of the electrolyte layer, which is beneficial to the efficient transport of ions and at the same time ensures the mechanical properties of the electrolyte layer.

[0026] In the second aspect of the present invention, the present invention provides a method for preparing the above-mentioned carbon mineralized structure supercapacitor, which can be referred to Figure 1 , and the method includes: (1) Coating the slurry obtained by mixing the carbon mineralized cementitious material, carbon conductive material, dispersant, and water on the surface of the foam metal, and then performing pre-pressing to form a pre-electrode; (2) Mixing and stirring the carbon mineralized cementitious material, bicarbonate, fibrous material, porous micro-nano material, air-entraining agent, and inorganic salt aqueous solution to obtain an electrolyte slurry; (3) Placing the pre-electrode on the upper and lower layers of the mold, and placing the electrolyte slurry in the middle of the mold, pressing and forming, and then performing carbonization treatment.

[0027] According to the preparation method of the above-mentioned carbon mineralized structure supercapacitor provided by the present invention, the slurry obtained by mixing the carbon mineralized cementitious material, carbon conductive material, dispersant, and water is coated on the surface of the foam metal. Under the action of the dispersant, the carbon conductive material is mixed more uniformly with the carbon mineralized cementitious material. After the subsequent carbonization treatment, the carbon conductive material can be evenly distributed in the three-dimensional space formed after the carbonization of the carbon mineralized cementitious material. Both the electrode and the electrolyte slurry use the carbon mineralized cementitious material. During the subsequent pressing and forming process, the electrode and the electrolyte will be in closer contact, significantly reducing the interfacial resistance between the two, thereby effectively improving the charge and discharge performance of the carbon mineralized structure supercapacitor.

[0028] In some embodiments of the present invention, in step (1), the mass ratio of the carbonated cementitious material to the water is 100:(15 - 25). For example, the mass ratios are 100:15, 100:18, 100:20, 100:22, 100:25, etc., or the ranges between any two of the above values. By controlling the mass ratio of the carbonated cementitious material to the water within the above range, the role of water as a CO2 transmission medium can be fully exerted, greatly accelerating the carbonation reaction rate of the carbonated cementitious material and forming a relatively high early strength.

[0029] In some embodiments of the present invention, the dispersant is selected from at least one of sodium dodecylbenzenesulfonate and polyvinylpyrrolidone. Preferably, the mass of the dispersant is 0.5% - 3% of the carbon conductive material; In some embodiments of the present invention, in step (2), the mass ratio of the carbonated cementitious material to the water in the inorganic salt aqueous solution is 100:(10 - 20). For example, the mass ratios are 100:10, 100:13, 100:15, 100:18, 100:20, etc., or the ranges between any two of the above values. By controlling the mass ratio of the carbonated cementitious material to the water in the inorganic salt aqueous solution within the above range, while accelerating the carbonation rate and strength formation, it can also strengthen the bonding with the electrode and enhance the ion transport efficiency in the electrolyte.

[0030] In some embodiments of the present invention, in step (3), the pressure for pressing and forming is 10 MPa - 30 MPa, and the pressure holding time is 3 min - 5 min.

[0031] In some embodiments of the present invention, the CO2 concentration in the carbonation curing device used for the carbonation treatment is ≥99%, the pressure is 0.2 MPa - 0.3 MPa, and the preset age is 24 h - 72 h.

[0032] In the third aspect of the present invention, the present invention proposes the application of the above carbonated structure supercapacitor or the carbonated structure supercapacitor prepared by the above method in the fields of aerospace, automotive, or construction.

[0033] The present invention has at least the following technical effects: (1) The structural electrode of the present invention is formed by carbonizing the composite of the carbonated cementitious material, the carbon conductive material, and the foam metal. The electrode material has high strength, a large specific surface area, and good electrical conductivity, which can greatly improve the capacitance of the structural supercapacitor.

[0034] (2) The solid electrolyte layer of the present invention is formed by carbonizing the composite of carbonated cementitious materials, bicarbonate, fibrous materials, porous micro-nano materials, air-entraining agents, and aqueous inorganic salt solutions. The mechanical properties and electrochemical properties of the solid electrolyte layer are balanced, forming a high-strength and efficient ion transport channel with an ionic conductivity of up to 50 mS / cm.

[0035] (3) The high-strength structural supercapacitor prepared based on the carbonated cementitious material system of the present invention breaks through the bottleneck of low strength and poor energy storage performance of traditional cement-based capacitors. Applying the carbonated cementitious material to the structure-energy storage integrated device, the carbonization strength can reach 40 MPa in 24 hours (at least 60% higher than the traditional one), and the specific capacitance ≥ 80 mF / cm 2 , the capacity retention rate is ≥ 90% after 5000 cycles, and it has low cost and environmental friendliness, and is expected to realize the integration of structure and function for energy storage in green buildings. Brief Description of the Drawings

[0036] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the following drawings are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0037] Figure 1 It is a schematic flow chart for preparing a structural supercapacitor according to an embodiment of the present invention; Figure 2 It is an electrochemical AC impedance curve diagram of each structural solid electrolyte layer in Examples 1, 2, 3, and 4; Figure 3 It is an electrochemical AC impedance curve diagram of each structural electrode in Examples 1, 2, 3, and 4; Figure 4 It is a cyclic voltammetry curve diagram of the structural supercapacitor in Example 3; Figure 5 It is a diagram of the specific capacitance and Coulomb efficiency of the structural supercapacitor in Example 3. Detailed Description of the Embodiments

[0038] Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention. The following describes the present invention with reference to specific embodiments. It should be noted that these embodiments are only descriptive and do not limit the present invention in any way.

[0039] Example 1 (1) Weigh 5 g of carbon mineralized cementitious material (including β-C2S, γ-C2S, C3S2, and CS, with a mass ratio of 4:2:3:1 and a residue on 80-μm sieve <1%), 0.2 g of carbon black, and mix them dry and evenly for standby. Weigh 0.001 g of sodium dodecylbenzenesulfonate, pour it into 0.75 g of water, stir, then pour it into the mixture, continue to stir, and divide the mixture into two parts, which are respectively coated on nickel foam and pre-pressed into shape for use as electrode materials; (2) Weigh 10 g of carbon mineralized cementitious material, 0.2 g of sodium bicarbonate, 1 g of polypropylene fiber, 0.25 g of porous silica, and 0.0025 g of air-entraining agent (sodium alkylbenzenesulfonate), and mix them dry and evenly for standby. Weigh 0.5 g of NaCl and dissolve it in 1 g of water, then pour the NaCl aqueous solution into the mixture and stir well to form an electrolyte slurry; (3) Place the obtained electrode materials on the upper and lower sides of the mold, place the electrolyte slurry in the middle, then apply a pressure of 30 MPa and hold the pressure for 3 min to press into a sandwich laminated structure, and place it in a carbonization curing device with a CO2 concentration ≥99% and a pressure of 0.3 MPa for curing for 24 h to obtain a carbon mineralized cementitious structure supercapacitor.

[0040] Example 2 (1) Weigh 5 g of carbon mineralized cementitious material (the same as in Example 1), 0.3 g of carbon nanotubes, and mix them dry and evenly for standby. Weigh 0.005 g of sodium dodecylbenzenesulfonate, pour it into 1 g of water, stir, then pour it into the mixture, continue to stir, and divide the mixture into two parts, which are respectively coated on nickel foam and pre-pressed into shape for use as electrode materials; (2) Weigh 10 g of carbon mineralized cementitious material, 0.25 g of sodium bicarbonate, 0.5 g of polypropylene fiber, 0.5 g of porous silica, and 0.0035 g of air-entraining agent (sodium alkyl sulfonate), and mix them dry and evenly for standby. Weigh 0.5 g of Na2SO4 and dissolve it in 1 g of water, then pour the Na2SO4 aqueous solution into the mixture and stir well to form an electrolyte slurry; (3) Place the obtained electrode materials on the upper and lower sides of the mold, place the electrolyte slurry in the middle, then apply a pressure of 30 MPa and hold the pressure for 3 min to press into a sandwich laminated structure, and place it in a carbonization curing device with a CO2 concentration ≥99% and a pressure of 0.3 MPa for curing for 24 h to obtain a carbon mineralized cementitious structure supercapacitor.

[0041] Example 3 (1) Weigh 5 g of carbon mineralized cementitious material (the same as in Example 1), 0.1 g each of carbon black, carbon nanotubes, and graphene, and mix them dry and evenly for standby. Weigh 0.003 g of sodium dodecylbenzenesulfonate, pour it into 1.25 g of water, stir, then pour it into the mixture, continue to stir, and divide the mixture into two parts, which are respectively coated on nickel foam and pre-pressed into shape for use as electrode materials; (2)Weigh 10 g of carbon mineralized cementitious material, 0.5 g of sodium bicarbonate, 0.15 g of polypropylene fiber, 0.35 g of porous CaCO3, and 0.004 g of air-entraining agent (alkyl sulfonate), and mix them evenly for later use. Weigh 0.5 g of KCl and dissolve it in 1 g of water, then pour the KCl aqueous solution into the mixture and stir well to form an electrolyte slurry; (3)Place the obtained electrode materials on the upper and lower sides of the mold, put the electrolyte slurry in the middle, then apply a pressure of 30 MPa and hold the pressure for 3 min to press into a sandwich laminate structure, and place it in a carbonization curing device with a CO2 concentration ≥ 99% and a pressure of 0.3 MPa for curing for 24 h to obtain a carbon mineralized cementitious structure supercapacitor.

[0042] Example 4 (1)Weigh 5 g of carbon mineralized cementitious material (the same as in Example 1), 0.15 g of carbon black and graphene each, mix them evenly for later use, weigh 0.003 g of polyvinylpyrrolidone, pour it into 0.75 g of water, stir, then pour it into the mixture, continue to stir, and divide the mixture into two parts, which are respectively coated on nickel foam and pre-pressed into shape for use as electrode materials; (2)Weigh 10 g of carbon mineralized cementitious material, 0.2 g of sodium bicarbonate, 0.2 g of glass fiber, 0.1 g of porous silica, 0.0025 g of air-entraining agent (rosin soap), and mix them evenly for later use. Weigh 0.4 g of NaCl and dissolve it in 1 g of water, then pour the NaCl aqueous solution into the mixture and stir well to form an electrolyte slurry; (3)Place the obtained electrode materials on the upper and lower sides of the mold, put the electrolyte slurry in the middle, then apply a pressure of 30 MPa and hold the pressure for 3 min to press into a sandwich laminate structure, and place it in a carbonization curing device with a CO2 concentration ≥ 99% and a pressure of 0.3 MPa for curing for 24 h to obtain a carbon mineralized cementitious structure supercapacitor.

[0043] Comparative Example 1 Based on Example 3, all of the carbon mineralized cementitious material therein was replaced with ordinary Portland cement for synthesis and testing.

[0044] Measure the performance of the structure supercapacitors provided in the examples and comparative examples as follows: (1)Test the ionic conductivity of the solid electrolyte layer of the structure supercapacitors in the examples and comparative examples.

[0045] The test results of the electrochemical impedance spectroscopy are as Figure 2 shown, from Figure 2It can be clearly seen that the resistance reduction effect in Example 3 is the best, which is beneficial to reducing the ion transport resistance in the electrolyte. Among them, sodium bicarbonate, air-entraining agent and porous micro-nano materials play a key role, optimizing the pore structure and ion transport channels of the solid electrolyte layer. Table 1 shows the ionic conductivities of the solid electrolyte layers in Examples 1-4 and Comparative Example 1, all of which reach 50 mS·cm -1 above, and the result in Example 3 is the best.

[0046] Table 1

[0047] (2)Compressive strength test of the solid electrolyte layer of the structural supercapacitor in the examples and comparative examples.

[0048] The universal testing machine was used to test the compressive strength of the solid electrolyte layers of Examples 1-4 and Comparative Example 1, and the loading speed was 2.4 KN / s. The results are shown in Table 2. It can be seen from the data that the carbon mineralized cementitious material as the core of the strength matrix is generally beneficial to the increase of mechanical properties, and the strength grade is significantly higher than that of ordinary Portland cement. Even with the introduction of pore-forming materials, the compressive strength after carbonization for 24 h can still be maintained above 40 MPa, and the flexural strength can be maintained above 8 MPa. The fibrous materials play an important role in this. The compressive strength of Example 3 is relatively smaller than that of other examples, mainly because the content of air-entraining agent and bicarbonate increases, forming more pore structures, thus resulting in a slight decrease in mechanical properties. And when the carbon mineralized cementitious material is replaced by ordinary Portland cement, that is, the strength of Comparative Example 1 is significantly lower than the strength of the solid electrolyte layer of this application.

[0049] Table 2

[0050] (3)Specific capacitance test of the structural supercapacitor of the structural supercapacitor in the examples and comparative examples.

[0051] The specific capacitances of the structural supercapacitors of Examples 1-4 and Comparative Example 1 were measured at 0.1 mA·cm -2 respectively, as shown in Table 3. It can be seen that the multi-dimensional carbon conductive material has a large specific surface area, and the combination of appropriate dosages helps to construct a three-dimensional point-line-plane conductive network, greatly improving the conductivity of the carbon mineralized structure electrode (such as Figure 3The ability to store electric charges as shown). However, excessive carbon conductive materials may lead to agglomeration, which is not conducive to improving the electrochemical performance of the electrode. In addition, adding appropriate amounts of sodium bicarbonate, air-entraining agents, and porous micro-nano materials can improve the specific capacitance of the capacitor. However, adding too much micro-nano material such as porous calcium carbonate or porous silica, etc., the carbonized matrix may agglomerate and affect the pore structure, resulting in a decrease in specific capacitance. The capacitor prepared with the traditional ordinary Portland cement material in Comparative Example 1 has a significantly lower specific capacitance than the capacitor of the present invention.

[0052] Table 3

[0053] (4)Test the cycling performance of the structural supercapacitor prepared in Example 3.

[0054] Taking the structural supercapacitor of Example 3 as an example, its cyclic voltammetry (CV) curve was tested, as Figure 4 shown. From Figure 4 it can be seen that the shape of the CV curve is approximately symmetric. As the scanning rate increases, the current at the same potential also increases accordingly, indicating that the capacitor has good cycling reversibility. In addition, at a constant current density of 0.1 mA·cm -2 , the capacitor was tested for 5000 constant current charge and discharge cycles, and its specific capacitance and Coulomb efficiency are as Figure 5 shown. The results show that after 5000 charge and discharge cycles, the capacitance of the structural supercapacitor shows a small decrease, and the capacitance retention rate is 91.02%. Its Coulomb efficiency is relatively stable and can still reach 95.82% after 5000 cycles, indicating that the structural capacitor of the present invention has good cycling stability and Coulomb efficiency.

[0055] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A carbon mineralized structure supercapacitor, characterized in that: include: An electrode, the electrode comprising a carbon mineralized gel material, a carbon conductive material and a foam metal, wherein the carbon conductive material is distributed in a three-dimensional space formed after the carbon mineralized gel material is carbonized and covers the foam metal together; The solid electrolyte layer, the electrodes are arranged on both sides of the solid electrolyte layer, the raw materials for preparing the solid electrolyte layer include: carbon mineralized gelling material, bicarbonate, fiber material, porous micro-nano material, air entraining agent and inorganic salt aqueous solution, and the raw materials for preparing the solid electrolyte layer are mixed, pressed and carbonized to form a solid electrolyte layer.

2. The carbon mineralized structure supercapacitor according to claim 1, characterized in that: The mass ratio of the carbon mineralized gelling material to the carbon conductive material is 100:(0.5-10); And / or, the carbon conductive material is selected from at least one of carbon black, carbon nanotubes, carbon fibers, and graphene.

3. The carbon mineralized structure supercapacitor according to claim 1 or 2, characterized in that: The thickness of the foam metal is 1 mm to 2 mm; preferably, the foam metal is selected from foam nickel, foam iron or foam copper; And / or, the thickness of the electrode is 2 mm-5 mm.

4. The carbon mineralized structure supercapacitor according to claim 1, characterized in that: The carbon mineralized cementitious material comprises β-C2S, γ-C2S, C3S2 and CS, preferably, the total content of β-C2S and C3S2 is not less than 70wt%, and the 80μm sieve residue rate is less than 1%; And / or, the thickness of the solid electrolyte layer is 3 mm-20 mm.

5. The carbon mineralized structure supercapacitor according to claim 1 or 2, characterized in that: The bicarbonate is selected from at least one of NaHCO3, KHCO3 and NH4HCO3; And / or, the fiber material is selected from at least one of polypropylene fiber and glass fiber, and preferably the fiber diameter of the fiber material is less than 30 μm and the length is less than 1 mm; And / or, the porous micro-nano material is selected from at least one of porous calcium carbonate and porous silicon dioxide; And / or, the air entraining agent is selected from at least one of alkylbenzene sulfonate compounds and rosin resin compounds; And / or, the inorganic salt in the inorganic salt aqueous solution is selected from at least one of NaCl, Na2SO4, and KCl, preferably a neutral inorganic salt aqueous solution, and more preferably the concentration of the inorganic salt aqueous solution is 1 mol / L-2 mol / L.

6. The carbon mineralized structure supercapacitor according to claim 1 or 2, characterized in that: The mass of the bicarbonate is 1-5% of the carbon mineralized cementitious material; and / or, the mass of the fiber material is 1-15% of the carbon mineralized gelling material; and / or, the mass of the porous micro-nano material is 0.5-5% of the carbon mineralized gelling material; And / or, the mass of the air entraining agent is 0.005-0.05% of the carbon mineralized cementitious material.

7. A method for preparing the carbon mineralized structure supercapacitor according to any one of claims 1 to 6, characterized in that: include: (1) coating the slurry obtained by mixing carbon mineralized gelling material, carbon conductive material, dispersant and water on the surface of the foam metal, and then pre-pressing and forming to obtain a pre-electrode; (2) mixing and stirring the carbon mineralized gelling material, bicarbonate, fiber material, porous micro-nano material, air entraining agent and inorganic salt aqueous solution to obtain an electrolyte slurry; (3) The pre-electrodes are placed on the upper and lower layers of a mold, the electrolyte slurry is placed in the middle of the mold, pressed into shape, and then carbonized.

8. The method according to claim 7, characterized in that: In step (1), the mass ratio of the carbon mineralized gelling material to the water is 100:(15-25); And / or, the dispersant is selected from at least one of sodium dodecylbenzene sulfonate and polyvinyl pyrrolidone, and preferably the mass of the dispersant is 0.5%-3% of the carbon conductive material; And / or, in step (2), the mass ratio of the carbon mineralized gelling material to the water in the inorganic salt aqueous solution is 100:(10-20).

9. The method according to claim 7, characterized in that: The compression molding pressure in step (3) is 10MPa-30MPa, and the holding time is 3min-5min; And / or, the CO2 concentration in the carbonization curing device used in the carbonization treatment is ≥99%, the pressure is 0.2MPa-0.3MPa, and the preset age is 24h-72h.

10. Application of the carbon mineralized structure supercapacitor according to any one of claims 1 to 6 or the carbon mineralized structure supercapacitor prepared by the method according to any one of claims 7 to 9 in the aerospace field, the automotive field or the construction field.

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