Cement-based zinc ion hybrid capacitor, preparation method thereof and application thereof in energy storage device

Abstract

The application provides a cement-based zinc ion hybrid capacitor, a preparation method thereof and application of the capacitor in an energy storage device. The cement-based zinc ion hybrid capacitor comprises an active carbon positive electrode, a zinc foil negative electrode and a composite air-entraining mortar interlayer arranged between the two electrodes. The active carbon positive electrode is active carbon loaded on a carrier with good conductivity, and the carrier is any one of carbon-based materials such as carbon felt, carbon fiber and graphite plate or any one of foils, meshes and foams of metals such as stainless steel, copper, titanium and nickel and alloys thereof. The composite air-entraining mortar interlayer between the two electrodes is immersed in an electrolyte under negative pressure. The composite air-entraining mortar has interconnected pores, and ions are transmitted through the electrolyte in the pores and participate in electrode reactions. The application mainly provides a porous cement-based solid electrolyte based on a composite air-entraining technology and a structural electrochemical energy storage device, and the structural energy storage device can simultaneously have good energy storage characteristics and mechanical properties.

Description

Technical Field

[0001] The present invention belongs to the technical field of capacitors, and in particular relates to a cement-based zinc ion hybrid capacitor, a preparation method thereof, and an application thereof in an energy storage device. Background Art

[0002] There is a growing demand for renewable energy to replace fossil fuels in the traditional energy mix. However, clean energy sources like photovoltaics and wind power are characterized by high volatility, high randomness, and significant intermittency. Their generation patterns are significantly affected by the natural environment, especially peak power generation, which often struggles to align with peak electricity demand. Forced integration into the grid can have a significant impact on the power supply system. Therefore, there is an urgent need to develop a new energy storage method suitable for large-scale deployment.

[0003] As a porous medium, concrete possesses a rich pore structure and a certain concentration of pore solution, providing essential properties for use as a carrier for battery electrolyte solutions. Furthermore, concrete is the world's most widely used building material. Combining hybrid capacitors with concrete to create a structural energy storage device can minimize the space occupied by the energy storage device, achieving the integration of structural strength and energy storage functionality.

[0004] Currently, the electrochemical system for cement-based energy storage devices is primarily supercapacitors. Due to factors such as a low voltage window, low material energy density, and low areal loading capacity, existing cement-based energy storage devices often have low energy density, making them difficult to meet practical needs.

[0005] For example, CN115424868A provides a graphene-coated nickel foam / cement structure supercapacitor, whose surface energy density is only 0.03Wh / m 2 , it is difficult to meet the basic needs of building energy storage.

[0006] Zinc-ion hybrid capacitors are asymmetric capacitors consisting of a zinc negative electrode and a double-layer capacitor positive electrode. In addition to the advantages of traditional supercapacitors such as high power density and long cycle life, hybrid capacitors have a higher voltage window and higher energy density. On the other hand, compared with alkaline electrolytes represented by KOH, zinc-ion hybrid capacitors using neutral to weakly acidic zinc salt solutions represented by zinc sulfate have higher energy density and longer cycle life.

[0007] However, high-concentration zinc salt solutions have high viscosity, making it difficult to fill the pores of cement mortar. Furthermore, they easily react with alkaline cement hydration products, reducing the strength and durability of the cement matrix. Therefore, preparing cement-based materials saturated with zinc salts and exhibiting high electrical conductivity while minimizing the damage to the mechanical properties of the cement matrix caused by zinc salts is both a challenge and a key issue in the preparation of structural zinc ion hybrid capacitors. Summary of the Invention

[0008] To address the problem that existing cement-based energy storage devices often have low energy density and are unable to meet user requirements, the present invention provides a cement-based zinc ion hybrid capacitor, a preparation method, and its application in energy storage devices. This invention primarily provides a porous cement-based solid electrolyte and its structural electrochemical energy storage device based on composite air entrainment technology. This structural energy storage device achieves both excellent energy storage characteristics and mechanical properties.

[0009] The cement-based zinc ion hybrid capacitor of the present invention comprises a tab, an activated carbon positive electrode, a zinc foil negative electrode, and a composite air-entraining mortar interlayer arranged between the two electrodes;

[0010] The tabs are fixedly connected to the activated carbon positive electrode and the zinc foil negative electrode respectively;

[0011] The activated carbon positive electrode is activated carbon loaded on a carrier with good conductivity, and the carrier is a carbon-based material such as carbon felt, carbon fiber, graphite plate, or any one of metals such as stainless steel, copper, titanium, nickel, and their alloys in foil, mesh, or foam form;

[0012] The composite air-entraining mortar interlayer between the two electrodes is immersed in the electrolyte under negative pressure; the composite air-entraining mortar has interconnected pores inside, and ions are transmitted through the electrolyte in the pores and participate in the electrode reaction.

[0013] Furthermore, the carrier used for the activated carbon positive electrode has a thickness of 0.01 to 1.0 mm, preferably 0.04 to 0.6 mm; and a pore size of 0.01 to 0.5 mm, preferably 0.05 to 0.2 mm.

[0014] Activated carbon loading is 0.6~26.8mg / cm 2 , preferably 1.2 to 14.2 mg / cm 2 .

[0015] The electrolyte solute is one or more soluble zinc salts such as zinc trifluoromethanesulfonate, zinc sulfate, zinc acetate, zinc nitrate, etc., and the zinc ion concentration is 0.1 to 4 mol / L, preferably 0.5 to 2 mol / L.

[0016] Furthermore, the electrolyte solute is zinc sulfate, and the zinc ion concentration is 0.1 to 4 mol / L, preferably 0.5 to 2 mol / L.

[0017] The thickness of the zinc foil is 10 to 100 μm, preferably 40 to 60 μm.

[0018] The tab material is one or more of aluminum, stainless steel, nickel, and titanium.

[0019] The present invention also provides a method for preparing the cement-based zinc ion hybrid capacitor, which includes preparing a composite air-entraining mortar interlayer and an activated carbon electrode.

[0020] The composite air-entraining mortar barrier layer comprises a composite air-entraining agent and cement mortar;

[0021] The composite air entraining agent is a combination of a physical air entraining agent and a chemical air entraining agent; the physical air entraining agent is sodium lauryl sulfate, and the addition amount is 0.001% to 0.04% of the cement mass, preferably 0.01% to 0.02%; the chemical air entraining agent is aluminum powder, and the addition amount is 0.1% to 0.5% of the cement mass, preferably 0.2% to 0.4%.

[0022] The cement mortar comprises cement, water and sand; and the mass ratio of cement, water and sand is 1: (0.4-0.9): 1, preferably 1: (0.7-0.8): 1.

[0023] The specific preparation process of the composite air-entraining mortar barrier is as follows:

[0024] S1: dissolving a physical air-entraining agent in water to obtain a solution, mixing the obtained solution with cement mortar and stirring to obtain a slurry, and then adding a chemical air-entraining agent to the slurry and stirring rapidly;

[0025] S2: The slurry obtained in S1 is placed in a mold and cured in a curing chamber to obtain a mortar specimen. The mold is then removed to obtain the specimen, which is then dried in a vacuum drying oven. The dried specimen is immersed in an electrolyte solution and the electrolyte solution is introduced into the mortar specimen by low-pressure infiltration. After the low-pressure infiltration is completed, the specimen is further immersed in the electrolyte solution for curing. The vacuum degree of the low-pressure infiltration is not less than -0.1 MPa.

[0026] Furthermore, in step S1, the obtained solution is mixed with cement mortar and stirred, and the stirring process is first slow stirring and then fast stirring, the slow stirring time is 20 to 40 seconds, and the fast stirring time is 80 to 100 seconds.

[0027] Furthermore, in step S1, the stirring time after adding the aluminum powder is 20 to 40 seconds.

[0028] Furthermore, in step S2, the temperature of the curing room is 18-22°C and the relative humidity is 90%-96%.

[0029] Furthermore, in step S2, the temperature of the vacuum drying oven is 40-50°C.

[0030] The method for preparing an activated carbon electrode comprises the following steps: grinding a binder, a conductive agent, and activated carbon in a mortar to obtain a dry material; adding N-methylpyrrolidone to the dry material and rapidly stirring to obtain a slurry; applying the resulting slurry to a conductive carrier, smoothing it with a scraper, and then drying it in an air drying oven.

[0031] The binder is selected from one or more of polyvinylidene fluoride, sodium alginate, polyvinyl alcohol, and hydroxymethyl cellulose.

[0032] The conductive agent is selected from one or more of acetylene black, Ketjen black, conductive graphite, and nano-carbon fiber.

[0033] The binder is polyvinylidene fluoride.

[0034] The conductive agent is acetylene black.

[0035] The mass ratio of the conductive agent, the binder and the activated carbon is (10-30): (10-30): (70-90).

[0036] The drying temperature of the blast drying oven is 50-70°C, and the drying time is 10-14 hours.

[0037] The preparation method of the cement-based zinc ion hybrid capacitor comprises the following steps: fixing the tabs with the activated carbon positive electrode and the zinc foil negative electrode, attaching the activated carbon positive electrode and the zinc foil negative electrode to both sides of the obtained composite air-entraining mortar interlayer, fixing them with tape, and then sealing to obtain the cement-based zinc ion hybrid capacitor.

[0038] Furthermore, the sealing method is one of vacuum packaging, epoxy coating, and paraffin coating.

[0039] This invention can be used to construct large-scale energy storage buildings, which have a positive effect on the storage of new energy sources such as photovoltaics and wind power. In particular, in eastern China, where land resources are in short supply, the combination of energy storage buildings and new energy sources such as photovoltaics and wind power can achieve smooth output of new energy sources such as photovoltaics and wind power, meeting the requirements for stable and safe access to the power grid for new energy generation. In addition, in western China, where power grid coverage is difficult, energy storage buildings combined with abundant local wind and solar resources can achieve self-sufficiency in electricity, save the cost of energy storage facility construction, significantly improve the living standards of local people, and promote border construction and development.

[0040] Compared with the prior art, the beneficial effects of the present invention are embodied in the following aspects:

[0041] (1) The present invention uses an activated carbon-coated nickel foam positive electrode and a zinc foil negative electrode connected to the tab as structural electrodes to construct a structural zinc ion hybrid capacitor. Compared with traditional supercapacitors, it has a higher voltage window and energy density and good cycle performance.

[0042] (2) The present invention introduces composite air entrainment into cement-based energy storage devices for the first time, improves the ionic conductivity of cement-based structural electrolytes, and enhances the strength of porous cement-based materials by vacuum immersion in ZnSO4 solution, while improving the electrical and mechanical properties of structural electrochemical energy storage devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 Schematic diagram of the structural energy storage device of the present invention.

[0044] Figure 2 This is the constant current charge and discharge curve of Example 1.

[0045] Figure 3 This is the cycle performance curve of Example 1.

[0046] Figure 4 This is the constant current charge and discharge curve of Example 2.

[0047] Figure 5 This is the cycle performance curve of Example 2.

[0048] Figure 6 This is the constant current charge and discharge curve of Example 3.

[0049] Figure 7 This is the cycle performance curve of Example 3.

[0050] Figure 8 This is the constant current charge and discharge curve of Example 4.

[0051] Figure 9 This is the cycle performance curve of Example 4.

[0052] Figure 10 This is the constant current charge and discharge curve of Example 5.

[0053] Figure 11 This is the cycle performance curve of Example 5.

[0054] Figure 12 This is the constant current charge and discharge curve of Example 6.

[0055] Figure 13 This is the cycle performance curve of Example 6.

[0056] Figure 14 This is the constant current charge and discharge curve of Example 7.

[0057] Figure 15 This is the cycle performance curve of Example 7.

[0058] Figure 16 This is the constant current charge and discharge curve of Example 8.

[0059] Figure 17 This is the cycle performance curve of Example 8.

[0060] Figure 18 This is the constant current charge and discharge curve of Example 9.

[0061] Figure 19 This is the cycle performance curve of Example 9.

[0062] Figure 20 This is the constant current charge and discharge curve of Example 10.

[0063] Figure 21 This is the cycle performance curve of Example 10.

[0064] Figure 22 This is the constant current charge and discharge curve of Example 11.

[0065] Figure 23 This is the cycle performance curve of Example 11.

[0066] Figure 24 This is the constant current charge and discharge curve of Example 12.

[0067] Figure 25 This is the cycle performance curve of Example 12.

[0068] Figure 26 This is the constant current charge and discharge curve of Example 13.

[0069] Figure 27 This is the cycle performance curve of Example 13.

[0070] Figure 28 This is the constant current charge and discharge curve of Example 14.

[0071] Figure 29 This is the cycle performance curve of Example 14.

[0072] Figure 30 This is the constant current charge and discharge curve of Example 15.

[0073] Figure 31 This is the cycle performance curve of Example 15.

[0074] Figure 32 This is the constant current charge and discharge curve of Example 16.

[0075] Figure 33 This is the cycle performance curve of Example 16.

[0076] Figure 34 This is the constant current charge and discharge curve of Example 17.

[0077] Figure 35 This is the cycle performance curve of Example 17.

[0078] Figure 36 This is the constant current charge and discharge curve of Example 18.

[0079] Figure 37 This is the cycle performance curve of Example 18.

[0080] Figure 38 This is the constant current charge and discharge curve of Example 19.

[0081] Figure 39 This is the cycle performance curve of Example 19. DETAILED DESCRIPTION

[0082] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0083] Example 1

[0084] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.05mm and a pore size of 0.08mm, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.8mg / cm3. 2 .

[0085] Dissolve 0.003g of sodium lauryl sulfate in 12g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0086] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimens were immersed in a 2M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimens were cured in the 2M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a sealing machine to create the structural energy storage device.

[0087] Example 2

[0088] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.05mm and a pore size of 0.08mm, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.8mg / cm3. 2 .

[0089] Dissolve 0.003g of sodium lauryl sulfate in 14g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0090] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimens were immersed in a 2M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimens were cured in the 2M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a sealing machine to create the structural energy storage device.

[0091] Example 3

[0092] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.05mm and a pore size of 0.08mm, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.8mg / cm3. 2 .

[0093] Dissolve 0.003g of sodium lauryl sulfate in 16g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0094] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimens were immersed in a 2M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimens were cured in the 2M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a sealing machine to create the structural energy storage device.

[0095] Example 4

[0096] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.05mm and a pore size of 0.08mm, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.8mg / cm3. 2 .

[0097] Dissolve 0.003g of sodium lauryl sulfate in 18g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0098] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimens were immersed in a 2M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimens were cured in the 2M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a sealing machine to create the structural energy storage device.

[0099] Example 5

[0100] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.05mm and a pore size of 0.08mm, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.8mg / cm3. 2 .

[0101] Dissolve 0.003g of sodium lauryl sulfate in 12g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.01g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0102] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimens were immersed in a 2M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimens were cured in the 2M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a sealing machine to create the structural energy storage device.

[0103] Example 6

[0104] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.05mm and a pore size of 0.08mm, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.8mg / cm3. 2 .

[0105] Dissolve 0.003g of sodium lauryl sulfate in 12g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.04g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0106] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimens were immersed in a 2M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimens were cured in the 2M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a sealing machine to create the structural energy storage device.

[0107] Example 7

[0108] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.05mm and a pore size of 0.08mm, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.8mg / cm3. 2 .

[0109] Dissolve 0.002g of sodium lauryl sulfate in 12g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0110] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimens were immersed in a 2M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimens were cured in the 2M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a sealing machine to create the structural energy storage device.

[0111] Example 8

[0112] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.05mm and a pore size of 0.08mm, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.8mg / cm3. 2 .

[0113] Dissolve 0.006g of sodium lauryl sulfate in 12g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0114] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimens were immersed in a 2M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimens were cured in the 2M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a sealing machine to create the structural energy storage device.

[0115] Example 9

[0116] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.05mm and a pore size of 0.08mm, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.8mg / cm3. 2 .

[0117] Dissolve 0.003g of sodium lauryl sulfate in 14g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.01g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0118] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimens were immersed in a 2M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimens were cured in the 2M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a sealing machine to create the structural energy storage device.

[0119] Example 10

[0120] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.05mm and a pore size of 0.08mm, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.8mg / cm3. 2 .

[0121] Dissolve 0.003g of sodium lauryl sulfate in 14g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.04g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0122] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimens were immersed in a 2M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimens were cured in the 2M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a sealing machine to create the structural energy storage device.

[0123] Example 11

[0124] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.05mm and a pore size of 0.08mm, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.8mg / cm3. 2 .

[0125] Dissolve 0.002g of sodium lauryl sulfate in 14g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0126] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimens were immersed in a 2M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimens were cured in the 2M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a sealing machine to create the structural energy storage device.

[0127] Example 12

[0128] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.05mm and a pore size of 0.08mm, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.8mg / cm3. 2 .

[0129] Dissolve 0.006g of sodium lauryl sulfate in 14g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0130] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimens were immersed in a 2M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimens were cured in the 2M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a sealing machine to create the structural energy storage device.

[0131] Example 13

[0132] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.05mm and a pore size of 0.08mm, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.8mg / cm3. 2 .

[0133] Dissolve 0.003g of sodium lauryl sulfate in 14g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0134] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing room for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimens were immersed in a 0.5 M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimens were cured in the 0.5 M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a sealing machine to create the structural energy storage device.

[0135] Example 14

[0136] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.05mm and a pore size of 0.08mm, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.8mg / cm3. 2 .

[0137] Dissolve 0.003g of sodium lauryl sulfate in 14g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0138] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing room for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimen was immersed in a 1M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimen was cured in the 1M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a packaging machine to create the structural energy storage device.

[0139] Example 15

[0140] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.06mm and a pore size of 0.11mm, flattened with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 3.2mg / cm3. 2 .

[0141] Dissolve 0.003g of sodium lauryl sulfate in 14g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0142] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimens were immersed in a 2M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimens were cured in the 2M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a sealing machine to create the structural energy storage device.

[0143] Example 16

[0144] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.045mm and a pore size of 0.06mm, flattened with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.4mg / cm3. 2 .

[0145] Dissolve 0.003g of sodium lauryl sulfate in 14g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0146] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimens were immersed in a 2M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimens were cured in the 2M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a sealing machine to create the structural energy storage device.

[0147] Example 17

[0148] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a nickel foam with a thickness of 0.2mm and a pore size of 0.1mm, scraped flat with a spatula, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 6.8mg / cm3. 2 .

[0149] Dissolve 0.003g of sodium lauryl sulfate in 14g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0150] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimen was immersed in a 2M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimen was cured in the 2M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated nickel foam and zinc foil, connected to stainless steel tabs, were attached as structural electrodes to the sides of the resulting cement-based solid electrolyte, secured with tape, and sealed using a packaging machine to create the structural energy storage device.

[0151] Example 18

[0152] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a nickel foam with a thickness of 0.3mm and a pore size of 0.1mm, scraped flat with a spatula, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 9.4mg / cm3. 2 .

[0153] Dissolve 0.003g of sodium lauryl sulfate in 14g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0154] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimen was immersed in a 2M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimen was cured in the 2M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated nickel foam and zinc foil, connected to stainless steel tabs, were attached as structural electrodes to the sides of the resulting cement-based solid electrolyte, secured with tape, and sealed using a packaging machine to create the structural energy storage device.

[0155] Example 19

[0156] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a 0.5mm thick, 0.1mm pore-diameter nickel foam, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 12.2mg / cm3. 2 .

[0157] Dissolve 0.003g of sodium lauryl sulfate in 14g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0158] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimen was immersed in a 2M ZnSO₄ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimen was cured in the 2M ZnSO₄ electrolyte solution for another 28 days. Activated carbon-coated nickel foam and zinc foil, connected to stainless steel tabs, were attached as structural electrodes to the sides of the resulting cement-based solid electrolyte, secured with tape, and sealed using a packaging machine to create the structural energy storage device.

[0159] Example 20

[0160] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.05mm and a pore size of 0.08mm, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.8mg / cm3. 2 .

[0161] Dissolve 0.003g of sodium lauryl sulfate in 14g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0162] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing room for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimen was immersed in a 1M ZnCl₂ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimen was cured in the 1M ZnCl₂ electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a sealing machine to create the structural energy storage device.

[0163] Example 21

[0164] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.05mm and a pore size of 0.08mm, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.8mg / cm3. 2 .

[0165] Dissolve 0.003g of sodium lauryl sulfate in 14g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0166] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The samples were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimens were immersed in a 1M Zn(NO₃)₂ electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimens were cured in the 1M Zn(NO₃)₂ electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached as structural electrodes to the sides of the resulting cement-based solid electrolyte, secured with tape, and sealed using a packaging machine to create the structural energy storage device.

[0167] Example 22

[0168] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.05mm and a pore size of 0.08mm, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.8mg / cm3. 2 .

[0169] Dissolve 0.003g of sodium lauryl sulfate in 14g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0170] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The specimens were then cured in a curing chamber for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimens were immersed in a 1 M Zn(CH3COO)2 electrolyte solution and vacuum infiltrated for three days. After vacuum infiltration, the specimens were cured in the 1 M Zn(CH3COO)2 electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a packaging machine to create the structural energy storage device.

[0171] Example 23

[0172] 0.05g of polyvinylidene fluoride, 0.05g of a conductive agent, and 0.4g of activated carbon were ground in a mortar to obtain a dry material. 1800mL of N-methylpyrrolidone was added to the dry material and rapidly stirred to obtain a slurry. The resulting slurry was applied to a stainless steel mesh with a thickness of 0.05mm and a pore size of 0.08mm, smoothed with a scraper, and then dried in a 60°C forced air drying oven. The activated carbon loading was approximately 2.8mg / cm3. 2 .

[0173] Dissolve 0.003g of sodium lauryl sulfate in 14g of tap water. Mix the resulting solution with 20g of Portland cement and 20g of sand, stirring slowly for 30 seconds, then rapidly for 1.5 minutes. Add 0.02g of aluminum powder to the resulting slurry and stir rapidly for 1.5 minutes.

[0174] The flowing polymer cement electrolyte was placed in a 20×20×20 mm cubic stainless steel mold and a 1.3 mm diameter, 5 mm height polytetrafluoroethylene cylindrical mold for mechanical and electrochemical performance testing, respectively. The specimens were then cured in a curing room for one day. After curing, the portion of the mortar specimen protruding from the mold was cut away with a knife, then removed from the mold and dried in a 45°C vacuum drying oven. The dried specimens were immersed in a 1M Zn(CF3SO3)2 electrolyte solution and vacuum-infiltrated for three days. After vacuum infiltration, the specimens were cured in the 1M Zn(CF3SO3)2 electrolyte solution for another 28 days. Activated carbon-coated stainless steel mesh and zinc foil, connected to stainless steel tabs, were attached to the sides of the resulting cement-based solid electrolyte as structural electrodes. The electrodes were secured with tape and then sealed using a sealing machine to create the structural energy storage device.

[0175] Test example

[0176] In the following examples, when testing mechanical properties, the sample size was 20×20×20 mm, and a UTM5105 microcomputer-controlled electronic universal testing machine was used with a loading speed of 0.5 mm / min. Three samples were tested in each group, and the average value was taken.

[0177] During the electrochemical performance test, the sample size was a 13mm diameter and 5mm thick disc. The constant current charge and discharge curves and cycle performance curves were measured by the CT3001A blue battery test system. The results of the AC impedance spectroscopy (EIS) were measured by the CHI 660C electrochemical workstation. The frequency range of the test was 10 6~0.01Hz, process the Nyquist impedance curve displayed by the test results, take the intercept on the x-axis, which is the solution resistance R, and determine the ionic conductivity σ (mS / cm) of the electrolyte by the formula.

[0178] σ=L / RS

[0179] in

[0180] L—thickness of cement-based electrolyte (m);

[0181] R—Nyquist impedance curve intercept on the x-axis, that is, solution resistance R (Ω);

[0182] S—effective area of ​​cement-based electrolyte (m 2 )

[0183] Example 1 Detection

[0184] The mechanical properties of the energy storage device with the above structure were tested, and the compressive strength of the composite air-entraining mortar was found to be 20.6 MPa, indicating that the supercapacitor with this structure has good mechanical properties. Figure 2 The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance at a current density of 0.1A·g -1 When the discharge mass specific capacitance is 142F / g, the corresponding area specific capacitance is 0.40F / cm 2 . Figure 3 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1 When the maximum mass energy density is 63.1mWh / g, the corresponding area energy density is 1.77Wh / m 2 The energy decay after 300 cycles is 7.1%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 61.2 mS / cm.

[0185] Example 2 Detection

[0186] The mechanical properties of the above-mentioned structural energy storage device were tested, and the compressive strength of the composite air-entraining mortar was found to be 18.3 MPa, indicating that the supercapacitor of this structure has good mechanical properties. Figure 4 The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance at a current density of 0.1A·g -1 When the discharge mass specific capacitance is 158.0F / g, the corresponding area specific capacitance is 0.44F / cm 2 . Figure 5 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1When the maximum mass energy density is 70.2mWh / g, the corresponding area energy density is 1.97Wh / m 2 The energy decay after 300 cycles is 6.3%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 68.3 mS / cm.

[0187] Example 3 Detection

[0188] The mechanical properties of the energy storage device with the above structure were tested, and the compressive strength of the composite air-entraining mortar was found to be 17.4 MPa, indicating that the supercapacitor with this structure has good mechanical properties. Figure 6 The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance at a current density of 0.1A·g -1 When the discharge mass specific capacitance is 164.7F / g, the corresponding area specific capacitance is 0.46F / cm 2 . Figure 7 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1 When the maximum mass energy density is 73.2mWh / g, the corresponding area energy density is 2.05Wh / m 2 The energy decay after 300 cycles is 5.9%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 71.2 mS / cm.

[0189] Example 4 Detection

[0190] The mechanical properties of the above-mentioned structural energy storage device were tested, and the compressive strength of the composite air-entraining mortar was found to be 16.2 MPa, indicating that the supercapacitor of this structure has good mechanical properties. Figure 8 The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance at a current density of 0.1A·g -1 When the mass specific capacitance of the discharge section is 167.2F / g, the corresponding area specific capacitance is 0.47F / cm 2 . Figure 9 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1 When the maximum mass energy density is 74.3mWh / g, the corresponding area energy density is 2.08Wh / m 2 The energy decay after 300 cycles is 6.2%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 72.3 mS / cm.

[0191] Example 5 Detection

[0192] The mechanical properties of the above-mentioned structural energy storage device were tested, and the compressive strength of the composite air-entraining mortar was found to be 21.2 MPa, indicating that the structural supercapacitor has good mechanical properties. Figure 10 The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance at a current density of 0.1A·g -1 When the discharge mass specific capacitance is 116.6F / g, the corresponding area specific capacitance is 0.33F / cm 2 . Figure 11 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1 When the maximum mass energy density is 51.8mWh / g, the corresponding area energy density is 1.45Wh / m 2 The energy decay after 300 cycles is 5.7%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 50.4 mS / cm.

[0193] Example 6 Detection

[0194] The mechanical properties of the energy storage device with the above structure were tested, and the compressive strength of the composite air-entraining mortar was found to be 12.2 MPa, indicating that the supercapacitor with this structure has good mechanical properties. Figure 12 The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance at a current density of 0.1A·g -1 When the discharge mass specific capacitance is 176.9F / g, the corresponding area specific capacitance is 0.50F / cm 2 . Figure 13 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1 When the maximum mass energy density is 78.6mWh / g, the corresponding area energy density is 2.20Wh / m 2 The energy decay after 300 cycles is 6.5%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 76.5 mS / cm.

[0195] Example 15 Detection

[0196] The mechanical properties of the above-mentioned structural energy storage device were tested, and the compressive strength of the composite air-entraining mortar was found to be 18.3 MPa, indicating that the supercapacitor of this structure has good mechanical properties. Figure 30 The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance at a current density of 0.1A·g -1 When the discharge mass specific capacitance is 157.1F / g, the corresponding area specific capacitance is 0.50F / cm2 . Figure 31 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1 When the maximum mass energy density is 69.8mWh / g, the corresponding area energy density is 2.23Wh / m 2 The energy decay after 300 cycles is 7.6%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 68.3 mS / cm.

[0197] Example 16 Detection

[0198] The mechanical properties of the above-mentioned structural energy storage device were tested, and the compressive strength of the composite air-entraining mortar was found to be 18.3 MPa, indicating that the supercapacitor of this structure has good mechanical properties. Figure 32 The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance at a current density of 0.1A·g -1 When the discharge mass specific capacitance is 161.1F / g, the corresponding area specific capacitance is 0.39F / cm 2 . Figure 33 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1 When the maximum mass energy density is 71.6mWh / g, the corresponding area energy density is 1.72Wh / m 2 The energy decay after 300 cycles is 5.2%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 68.3 mS / cm.

[0199] Example 17 Detection

[0200] The mechanical properties of the above-mentioned structural energy storage device were tested, and the compressive strength of the composite air-entraining mortar was found to be 18.3 MPa, indicating that the supercapacitor of this structure has good mechanical properties. Figure 34 The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance at a current density of 0.1A·g -1 When the mass specific capacitance of the discharge section is 144.6F / g, the corresponding area specific capacitance is 0.98F / cm 2 . Figure 35 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1 When the maximum mass energy density is 64.3mWh / g, the corresponding area energy density is 4.37Wh / m 2The energy decay after 300 cycles is 10.3%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 68.3 mS / cm.

[0201] Example 7 Detection

[0202] The mechanical properties of the energy storage device with the above structure were tested, and the compressive strength of the composite air-entraining mortar was found to be 20.8 MPa, indicating that the supercapacitor with this structure has good mechanical properties. Figure 14 The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance at a current density of 0.1A·g -1 When the mass specific capacitance of the discharge section is 140.6F / g, the corresponding area specific capacitance is 0.39F / cm 2 . Figure 15 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1 When the maximum mass energy density is 62.5mWh / g, the corresponding area energy density is 1.75Wh / m 2 The energy decay after 300 cycles is 7.2%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 60.8 mS / cm.

[0203] Example 8 Detection

[0204] The mechanical properties of the energy storage device with the above structure were tested, and the compressive strength of the composite air-entraining mortar was found to be 19.1 MPa, indicating that the supercapacitor with this structure has good mechanical properties. Figure 16 The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance at a current density of 0.1A·g -1 When the discharge mass specific capacitance is 144.8F / g, the corresponding area specific capacitance is 0.41F / cm 2 . Figure 17 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1 When the maximum mass energy density is 64.3mWh / g, the corresponding area energy density is 1.80Wh / m 2 The energy decay after 300 cycles is 5.6%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 62.6 mS / cm.

[0205] Example 9 Detection

[0206] The mechanical properties of the energy storage device with the above structure were tested, and the compressive strength of the composite air-entraining mortar was found to be 18.9 MPa, indicating that the supercapacitor with this structure has good mechanical properties. Figure 18 The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance at a current density of 0.1A·g -1 When the discharge mass specific capacitance is 151.9F / g, the corresponding area specific capacitance is 0.43F / cm 2 . Figure 19 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1 When the maximum mass energy density is 67.5mWh / g, the corresponding area energy density is 1.89Wh / m 2 The energy decay after 300 cycles is 6.6%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 54.6 mS / cm.

[0207] Example 10 Detection

[0208] The mechanical properties of the energy storage device with the above structure were tested, and the compressive strength of the composite air-entraining mortar was found to be 10.1 MPa, indicating that the supercapacitor with this structure has good mechanical properties. Figure 20 The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance at a current density of 0.1A·g -1 When the discharge mass specific capacitance is 167.0F / g, the corresponding area specific capacitance is 0.47F / cm 2 . Figure 21 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1 When the maximum mass energy density is 74.2mWh / g, the corresponding area energy density is 2.08Wh / m 2 The energy decay after 300 cycles is 5.4%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 79.8 mS / cm.

[0209] Example 11 Detection

[0210] The mechanical properties of the energy storage device with the above structure were tested, and the compressive strength of the composite air-entraining mortar was found to be 18.5 MPa, indicating that the supercapacitor with this structure has good mechanical properties. Figure 22 The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance at a current density of 0.1A·g -1 When the discharge mass specific capacitance is 156.8F / g, the corresponding area specific capacitance is 0.44F / cm2 . Figure 23 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1 When the maximum mass energy density is 69.7mWh / g, the corresponding area energy density is 1.95Wh / m 2 The energy decay after 300 cycles is 6.7%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 67.3 mS / cm.

[0211] Example 12 Detection

[0212] The mechanical properties of the energy storage device with the above structure were tested, and the compressive strength of the composite air-entraining mortar was found to be 17.6 MPa, indicating that the supercapacitor with this structure has good mechanical properties. Figure 24 The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance at a current density of 0.1A·g -1 When the mass specific capacitance of the discharge section is 159.5F / g, the corresponding area specific capacitance is 0.45F / cm 2 . Figure 25 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1 When the maximum mass energy density is 70.9mWh / g, the corresponding area energy density is 1.99Wh / m 2 The energy decay after 300 cycles is 5.9%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 68.9 mS / cm.

[0213] Example 13 Detection

[0214] The mechanical properties of the energy storage device with the above structure were tested, and the compressive strength of the composite air-entraining mortar was found to be 16.4 MPa, indicating that the supercapacitor with this structure has good mechanical properties. Figure 26 The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance. When the current density is 0.1A·g-1, the mass specific capacitance of the discharge section is 118.5F / g, and the corresponding area specific capacitance is 0.33F / cm 2 . Figure 27 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1 When the maximum mass energy density is 52.7mWh / g, the corresponding area energy density is 1.48Wh / m 2 The energy decay after 300 cycles is 10.3%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 51.2 mS / cm.

[0215] Example 14 Detection

[0216] The mechanical properties of the energy storage device with the above structure were tested, and the compressive strength of the composite air-entraining mortar was found to be 17.3 MPa, indicating that the supercapacitor with this structure has good mechanical properties. Figure 28 The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance at a current density of 0.1A·g -1 When the mass specific capacitance of the discharge section is 123.6F / g, the corresponding area specific capacitance is 0.35F / cm 2 . Figure 29 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1 When the maximum mass energy density is 55.0mWh / g, the corresponding area energy density is 1.54Wh / m 2 The energy decay after 300 cycles is 8.2%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 53.4 mS / cm.

[0217] Example 18 Detection

[0218] The mechanical properties of the above-mentioned structural energy storage device were tested, and the compressive strength of the composite air-entraining mortar was found to be 18.3 MPa, indicating that the supercapacitor of this structure has good mechanical properties. Figure 36 The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance at a current density of 0.1A·g -1 When the mass specific capacitance of the discharge section is 140.1F / g, the corresponding area specific capacitance is 1.32F / cm 2 . Figure 37 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1 When the maximum mass energy density is 62.3mWh / g, the corresponding area energy density is 5.85Wh / m 2 The energy decay after 300 cycles is 15.4%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 68.3 mS / cm.

[0219] Example 19 Detection

[0220] The mechanical properties of the above-mentioned structural energy storage device were tested, and the compressive strength of the composite air-entraining mortar was found to be 18.3 MPa, indicating that the supercapacitor of this structure has good mechanical properties. Figure 36The constant current charge and discharge curve (GCD) has a voltage window of 0.2V to 1.8V, and has good electrical performance. 1 When the discharge mass specific capacitance is 133.4F / g, the corresponding area specific capacitance is 1.63F / cm 2 . Figure 37 The cycle performance diagram of the structural energy storage device is shown in Figure 2. At a current density of 0.1 A·g -1 When the maximum mass energy density is 59.3mWh / g, the corresponding area energy density is 7.23Wh / m 2 The energy decay after 300 cycles is 19.6%. According to the results of electrochemical impedance spectroscopy (EIS), the conductivity of the composite air-entraining cement-based solid electrolyte is 68.3 mS / cm.

Claims

1. A cement-based zinc ion hybrid capacitor, characterized in that: The composition includes a tab, an activated carbon positive electrode, a zinc foil negative electrode and a composite air-entraining mortar interlayer arranged between the two electrodes; the composite air-entraining mortar interlayer is immersed in an electrolyte; The tabs are fixedly connected to the activated carbon positive electrode and the zinc foil negative electrode respectively; The activated carbon positive electrode is activated carbon loaded on a conductive carrier, and the activated carbon loading is 0.6-26.8 mg / cm 2 ; The composite air-entraining mortar has interconnected pores inside, and ions are transported through the electrolyte in the pores and participate in the electrode reaction; The electrolyte solute is one or more of zinc trifluoromethanesulfonate, zinc sulfate, zinc acetate, and zinc nitrate, and the zinc ion concentration is 0.1 to 4 mol / L; The composite air-entraining mortar interlayer comprises raw materials including a composite air-entraining agent and cement mortar; the composite air-entraining agent is a combination of a physical air-entraining agent and a chemical air-entraining agent; the cement mortar comprises cement, water and sand; the physical air-entraining agent is sodium lauryl sulfate, and the chemical air-entraining agent is aluminum powder.

2. The cement-based zinc ion hybrid capacitor according to claim 1, characterized in that: The tab material is one or more of aluminum, stainless steel, nickel, and titanium.

3. The cement-based zinc ion hybrid capacitor according to claim 1, characterized in that: The carrier is a carbon-based material or a metal or an alloy thereof.

4. The cement-based zinc ion hybrid capacitor according to claim 3, characterized in that: The carbon-based material is selected from carbon felt, carbon fiber, and graphite plate.

5. The cement-based zinc ion hybrid capacitor according to claim 3, characterized in that: The metal material is selected from any one or combination of stainless steel, copper, titanium, nickel and alloys thereof in foil, mesh or foam form.

6. The cement-based zinc ion hybrid capacitor according to claim 1, characterized in that: The carrier used for the activated carbon positive electrode has a thickness of 0.01~1.0 mm and a pore size of 0.01~0.5 mm.

7. The cement-based zinc ion hybrid capacitor according to claim 1, characterized in that: The loading capacity of activated carbon is 1.2~14.2mg / cm 2 .

8. The cement-based zinc ion hybrid capacitor according to claim 1, characterized in that: The thickness of zinc foil is 10 ~100μm.

9. The cement-based zinc ion hybrid capacitor according to claim 1, characterized in that: The zinc ion concentration of the electrolyte solution is 0.5~2 mol / L.

10. The cement-based zinc ion hybrid capacitor according to claim 1, characterized in that: The electrolyte solute is zinc sulfate, and the zinc ion concentration is 0.1~4 mol / L.

11. The cement-based zinc ion hybrid capacitor according to claim 10, characterized in that: The dosage of physical air entraining agent is 0.01%~0.02% of cement mass; the dosage of chemical air entraining agent is 0.2%~0.4% of cement mass; The mass ratio of cement, water and sand is 1:(0.7~0.8):

1.

12. The method for preparing the cement-based zinc ion hybrid capacitor according to any one of claims 1 to 11, characterized in that: The tabs are fixedly connected to the activated carbon positive electrode and the zinc foil negative electrode; the activated carbon electrode and the zinc foil are attached to both sides of the composite air entraining mortar interlayer, fixed, and then sealed to obtain the cement-based zinc ion hybrid capacitor.

13. The method according to claim 12, characterized in that: The specific preparation process of the composite air-entraining mortar barrier is as follows: S1: dissolving a physical air-entraining agent in water to obtain a solution, mixing the obtained solution with cement mortar and stirring to obtain a slurry, and then adding a chemical air-entraining agent to the slurry and stirring rapidly; S2: The slurry obtained in S1 is placed in a mold, and the mortar specimen is cured in a curing room to obtain a mortar specimen. The mold is then removed to obtain the specimen, and the specimen is placed in a vacuum drying oven for drying. The dried specimen is immersed in an electrolyte solution, and the electrolyte solution is introduced into the mortar specimen by low-pressure infiltration. After the low-pressure infiltration is completed, the mortar specimen is continued to be immersed in the electrolyte solution for curing. The vacuum degree of the low-pressure infiltration is not less than -0.1 MPa.

14. The method according to claim 12, characterized in that: The method for preparing the activated carbon electrode comprises the following steps: grinding a binder, a conductive agent, and activated carbon in a mortar to obtain a dry material; adding N-methylpyrrolidone to the dry material and rapidly stirring to obtain a slurry; applying the obtained slurry to a conductive carrier, smoothing it with a scraper, and then drying it in a blast drying oven; The binder is selected from one or more of polyvinylidene fluoride, sodium alginate, polyvinyl alcohol, and hydroxymethyl cellulose; The conductive agent is selected from one or more of acetylene black, Ketjen black, conductive graphite, and nano-carbon fiber; The mass ratio of the conductive agent, the binder and the activated carbon is (10-30): (10-30): (70-90).

15. The method according to claim 14, characterized in that: The drying temperature of the blast drying oven is 50~70℃, and the drying time is 10~14h.

16. Use of the cement-based zinc ion hybrid capacitor according to any one of claims 1 to 11, characterized in that: As a building structure energy storage device.

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