High-strength energy-storing floor tile and preparation method and application thereof

Abstract

The application relates to a high-strength energy storage floor tile and a preparation method and application thereof. The floor tile comprises an energy storage sandwich and a high-strength shell coated outside, the energy storage sandwich comprises a cement-based electrolyte and positive and negative electrodes assembled on opposite sides of the cement-based electrolyte, and the high-strength shell is an ultra-high performance concrete-based shell. The specific steps of the preparation method are as follows: a porous cement-based electrolyte is constructed by adopting a freeze casting technology; a reticular electrode assembly is carried out, vanadium oxide is used as the positive electrode, and zinc sheet is used as the negative electrode; and the high-strength energy storage floor tile is obtained after being packaged by adopting the ultra-high performance concrete-based shell. Compared with the prior art, the application is combined with the freeze casting and the floor tile structure design, has high strength and also has matched energy storage performance, the energy storage floor tile is suitable for the field of building decoration, realizes the integration of decoration, energy storage and structural performance, and greatly improves the functionalization level of traditional building materials and low-carbon development.

Description

Technical Field

[0001] This invention relates to the field of electrochemical energy storage technology, and in particular to a high-strength energy storage floor tile, its preparation method, and its application. Background Technology

[0002] With the development of modern building technology, the functional performance requirements of building materials are increasingly higher. While traditional floor tiles perform well in terms of strength and durability, their function is limited and has significant room for improvement. As the demand for energy storage continues to increase, the development of low-carbon building materials with energy storage capabilities has gradually become a research hotspot. However, existing energy storage floor tile technology has not yet achieved commercial application, and research on energy storage materials based on cement or concrete is still in its early stages, facing numerous technical challenges. How to endow floor tiles with electrochemical storage functions while ensuring their mechanical properties is an important trend in the low-carbon development of building materials. Ionic conductivity is a key indicator for energy storage floor tiles. Currently, methods to improve ionic conductivity include adding ion-conducting additives, introducing polymer electrolytes, adding metal oxides or nanomaterials, and introducing liquid electrolytes. Adding ion-conducting additives may lead to corrosion of electrode materials and weaken the structural stability of the material. Polymer electrolytes are prone to decomposition and aging, affecting the long-term stability of energy storage floor tiles, and uneven distribution will significantly reduce their overall performance. Adding metal oxides or nanomaterials may face a significant increase in cost and may also result in uneven distribution. Using liquid electrolytes carries the risk of leakage, which could compromise the safety of energy storage pavers. Therefore, developing a high-strength energy storage paver with high ionic conductivity and high stability has become a current research hotspot. Summary of the Invention

[0003] The purpose of this invention is to provide a high-strength energy storage floor tile, its preparation method, and its application, thereby solving the problems of low ionic conductivity and stability of energy storage floor tiles in the prior art.

[0004] The objective of this invention can be achieved through the following technical solutions:

[0005] This invention provides a high-strength energy storage floor tile, comprising an energy storage core and a high-strength outer shell.

[0006] Preferably, the energy storage sandwich includes a cement-based electrolyte and positive and negative electrodes assembled on opposite sides of the cement-based electrolyte, and the high-strength outer shell is an ultra-high performance concrete-based outer shell.

[0007] Preferably, the cement-based electrolyte has an oriented pore structure with a pore size of 10-20 μm and a porosity of 25-40%.

[0008] Preferably, the positive and negative electrodes are mesh electrodes.

[0009] Preferably, the positive and negative electrodes are respectively disposed at both ends of the oriented hole structure.

[0010] Preferably, the length × width of the energy storage sandwich is (250-260) × (250-260) mm, and the vertical height is 5-7 mm.

[0011] More preferably, the energy storage sandwich has a length × width of 260 × 260 mm and a vertical height of 7 mm.

[0012] Preferably, the high-strength energy storage floor tile has a length × width of (290-300) × (290-300) mm and a vertical height of 13-15 mm.

[0013] More preferably, the high-strength energy storage floor tile has a length × width of 300 × 300 mm and a vertical height of 15 mm.

[0014] Preferably, the orientation of the oriented pore structure is consistent with the vertical direction of the cement-based electrolyte, and the positive and negative electrodes are respectively disposed on both sides of the vertical direction of the cement-based electrolyte.

[0015] Preferably, the cement-based electrolyte comprises the following components in parts by weight:

[0016]

[0017] More preferably, the cement-based electrolyte comprises the following components in parts by weight:

[0018]

[0019] Preferably, the ultra-high performance concrete base shell comprises the following components in parts by weight:

[0020]

[0021]

[0022] More preferably, the ultra-high performance concrete-based shell comprises the following components in parts by weight:

[0023]

[0024] Preferably, the cementing material is selected from any one or more of silicate cement, fly ash, and silica fume.

[0025] Preferably, the water-reducing agent is a polycarboxylate water-reducing agent.

[0026] Preferably, the modifier is polyacrylamide.

[0027] Preferably, the early strength agent is selected from any one or more of gypsum and water glass.

[0028] Preferably, the filler is selected from any one or more of silica fume, quartz sand, and quartz powder.

[0029] Secondly, the present invention also provides a method for preparing the above-mentioned high-strength energy storage floor tile, comprising the following steps:

[0030] S1: Mix the cementitious material, water-reducing agent, early strength agent and water until homogeneous, then add the modifier and mix until homogeneous to obtain slurry A;

[0031] S2: Pour slurry A into the energy storage sandwich mold and let it stand;

[0032] S3: Place the energy storage sandwich mold containing slurry A on an ultra-low temperature medium for cryogenic casting to obtain solidified energy storage sandwich material B;

[0033] S4: Thaw the solidified energy storage sandwich material B to obtain energy storage sandwich material C, and then place energy storage sandwich material C in a cement curing box for curing to obtain energy storage sandwich material D with directional pore structure;

[0034] S5: Immerse the energy storage sandwich material D with a directional pore structure into the electrolyte solution to obtain the energy storage sandwich material E with a directional pore structure, i.e., the cement-based electrolyte.

[0035] S6: Immerse the electrode material in liquid nitrogen solution for cooling and shrinkage, and then quickly splice the electrode with the energy storage sandwich material E with oriented pore structure to obtain the assembled energy storage sandwich F.

[0036] S7: Mix silicate cement and filler in proportion, add water-reducing agent and water mixture, and mix again to obtain slurry G;

[0037] S8: Place the energy storage core into a high-strength outer shell mold, pour in slurry G, so that the slurry G surrounds the energy storage core, and cure in a standard concrete curing box for 20-32 days to obtain the high-strength energy storage floor tile.

[0038] Preferably, in step S1, the mixing speed of the cementitious material, water-reducing agent, early-strength agent and water is 55-65 r / min, and the mixing time is 60-80 s.

[0039] Preferably, in step S1, the stirring speed after adding the modifier is 120-140 r / min, and the stirring time is 50-70 s.

[0040] Preferably, in step S2, the energy storage sandwich mold includes a high thermal conductivity platform, a grid base disposed on the high thermal conductivity platform, a low thermal conductivity frame disposed around the grid base, and a low thermal conductivity grid cover plate disposed on the low thermal conductivity frame. Only the high thermal conductivity platform of the energy storage sandwich mold is in contact with the cryogenic medium.

[0041] Preferably, in step S2, after pouring slurry A into the energy storage sandwich mold and covering it with a low thermal conductivity mesh cover, the slurry is left to stand for 8 to 15 seconds, more preferably 10 seconds.

[0042] Preferably, in step S3, the cryogenic casting time is 30-50 minutes, and the cryogenic casting time is closely related to the cryogenic medium and the energy storage sandwich material B.

[0043] More preferably, in step S3, the cryogenic medium is liquid nitrogen, and the temperature of the liquid nitrogen is -190 to -180°C.

[0044] More preferably, in step S3, when the vertical height of the energy storage sandwich material B is 7 mm, it needs to be freeze-cast for 30 minutes; when the vertical height of the energy storage sandwich material B is 20 mm, it needs to be freeze-cast for 50 minutes.

[0045] Preferably, in step S4, the thawing refers to placing the energy storage sandwich material B in a constant temperature environment of 0-4℃ for curing.

[0046] More preferably, when the vertical height of the energy storage sandwich material B is 5 mm, it needs to be cured for 18 hours.

[0047] More preferably, when the vertical height of the energy storage sandwich material B is 7 mm, it needs to be cured for 20 hours.

[0048] Preferably, in step S5, the electrolyte solution is a zinc sulfate solution, and the concentration of the zinc sulfate solution is 1-2M, more preferably 2M.

[0049] Preferably, in step S5, the immersion time is related to the vertical height of the energy storage sandwich material D. When the vertical height of the energy storage sandwich material D is 5 mm, it needs to be soaked for 24 hours. When the vertical height of the energy storage sandwich material D is 7 mm, it needs to be soaked for 48 hours. After taking it out, let it stand for 3 hours, and then wipe the surface liquid dry.

[0050] Preferably, in step S6, the electrode material is a mesh electrode, which includes a positive electrode and a negative electrode. The positive electrode is a vanadium oxide mesh electrode, and the negative electrode is a zinc mesh electrode. The electrode material is immersed in liquid nitrogen solution for 20-40 seconds to shrink.

[0051] Preferably, step S8 includes the following steps:

[0052] S8.1: Pour 35-50 wt% of slurry G into the high-strength shell mold. The height of the poured slurry G should be flush with the base in the high-strength shell mold.

[0053] S8.2: Place the assembled energy storage sandwich F on the base in the high-strength outer shell mold, pour in the remaining slurry G, so that the slurry G surrounds the energy storage sandwich, and cure it in a standard concrete curing box for 20-32 days to obtain the high-strength energy storage floor tile.

[0054] Preferably, in step S8.1, after pouring in the 35-50 wt% slurry G, the high-strength outer shell mold needs to be placed on a concrete vibrating table and vibrated for 20-40 seconds.

[0055] Preferably, in step S8.2, after pouring in the remaining slurry G, the high-strength outer shell mold needs to be placed on a concrete vibration table and vibrated for 40-60 seconds.

[0056] Preferably, the entire process of step S8 takes no more than 5 minutes to complete.

[0057] Thirdly, the present invention also provides an application of the above-mentioned high-strength energy storage floor tiles in the field of building decoration.

[0058] The high-strength energy-storage paving brick designed in this invention has a dual function. This dual function is reflected not only in its strength, wear resistance, and aesthetics as a paving material, but also in its energy storage properties. This paving brick can be integrated with landscape design, serving as a paving material for courtyards, walkways, plazas, etc., making it both practical and beautiful. It can not only store solar energy but also provide power for nighttime landscape lighting, thus effectively storing electrical energy.

[0059] The high-strength energy-storage floor tile designed in this invention has a built-in battery that stores and releases energy through charge exchange. During discharge, zinc loses electrons at the negative electrode, oxidizes to Zn2+, and enters the electrolyte; simultaneously, vanadium oxide accepts electrons at the positive electrode, forming V3+. During charging, zinc ions return to the negative electrode and accept electrons, reducing to zinc metal; V3+ loses electrons at the positive electrode, reverting to vanadium oxide. This reaction cycle allows the floor tile to provide traditional functions while also serving as a sustainable energy solution.

[0060] Compared with the prior art, the present invention has the following beneficial effects:

[0061] (1) The present invention prepares a high-strength energy storage brick by assembling a mesh electrode as an energy storage sandwich on the surface of a cement-based electrolyte with a directionally arranged pore structure and using ultra-high performance concrete as a high-strength shell. The high-strength energy storage brick has high ionic conductivity and high stability.

[0062] (2) This invention constructs directional channels inside high-strength concrete through freeze casting. This directional channel design not only effectively improves the migration rate of ions, but also ensures that the overall performance of the material is not impaired by the introduction of pores. The use of a special mesh mold reduces the interfacial impedance between the cement-based electrolyte and the electrode.

[0063] (3) The high-strength energy storage floor tile of the present invention uses an ultra-high performance concrete matrix as a high-strength shell, which not only prevents electrolyte leakage, but also further improves the toughness and load-bearing capacity of the floor tile, giving it high mechanical properties. It can be applied in the construction field, realizing the integration of decoration, energy storage and structural performance, and greatly improving the functional level of traditional building materials.

[0064] (4) The high-strength energy storage floor tiles of the present invention use solid waste, such as fly ash and silica fume, to achieve high strength and energy storage functions while reducing waste disposal, promoting the low-carbon development of traditional building materials, and providing new solutions for future smart buildings and sustainable development. Attached Figure Description

[0065] Figure 1 This is a schematic diagram of the overall structure of the energy storage sandwich mold for the high-strength energy storage floor tile of the present invention.

[0066] Figure 2 This is a schematic diagram of the low thermal conductivity grid cover plate of the energy storage sandwich mold for the high-strength energy storage floor tile of the present invention.

[0067] Figure 3 This is a schematic diagram of the internal structure of the energy storage sandwich mold for the high-strength energy storage floor tile of the present invention.

[0068] Figure 4 This is a schematic diagram of the energy storage sandwich assembly of the high-strength energy storage floor tile of the present invention;

[0069] Figure 5 This is a schematic diagram of the high-strength outer shell mold for the high-strength energy storage floor tile of the present invention;

[0070] Figure 6 This is a schematic diagram (front view) of the high-strength energy storage floor tile according to Embodiment 1 of the present invention (in the figure, h = 15mm, m = 4mm, n = 7mm);

[0071] Figure 7 This is a top view of the high-strength energy storage floor tile according to Embodiment 1 of the present invention (in the figure, a = 300 mm, b = 280 mm, c = 20 mm);

[0072] In the diagram: 1-High thermal conductivity platform; 2-Grid base; 3-Low thermal conductivity frame; 4-Low thermal conductivity grid cover; 5-Energy storage sandwich mold; 6-Base; 7-High strength outer shell mold; H-Zinc mesh electrode; I-Vanadium oxide mesh electrode; E-Cement-based electrolyte; F-Energy storage sandwich; J-High strength outer shell. Detailed Implementation

[0073] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0074] Unless otherwise specified, the reagents, methods, instruments, and equipment used in this invention are conventional in the art. Unless otherwise specified, the reagents and materials used in the following examples are all commercially available.

[0075] Example 1

[0076] A high-strength energy storage floor tile includes an energy storage core and a high-strength outer shell.

[0077] like Figure 4 As shown, the energy storage sandwich includes a cement-based electrolyte and positive and negative electrodes assembled on opposite sides of the cement-based electrolyte, and the high-strength outer shell is an ultra-high performance concrete-based outer shell.

[0078] The cement-based electrolyte comprises the following components in parts by weight:

[0079] 70 parts of cementitious material;

[0080]

[0081] The ultra-high performance concrete shell comprises the following components in parts by weight:

[0082]

[0083] In this embodiment, the positive electrode is a vanadium oxide mesh electrode, and the negative electrode is a zinc mesh electrode.

[0084] In this embodiment, the cementitious material comprises the following components in parts by weight: 80% silicate cement, 10% fly ash, and 10% silica fume; the water-reducing agent is a polycarboxylate water-reducing agent, specifically a high-early-strength polycarboxylate water-reducing agent; the modifier is polyacrylamide (weight-average molecular weight of 10 million Daltons); the early-strength agent comprises the following components in parts by weight: 50% gypsum and 50% water glass, wherein the modulus of the water glass is 2.5. The filler comprises the following components in parts by weight: 20% silica fume, 72% quartz sand with a particle size of 0.4-1 mm, and 8% quartz powder with a particle size of 5-100 micrometers.

[0085] The preparation process of the high-strength energy storage floor brick is as follows: First, 70 parts of cementitious material, 0.18 parts of water-reducing agent, 5.25 parts of early-strength agent, and 35 parts of water are placed in a mixing pot and mixed evenly. Then, 0.11 parts of modifier are placed in the mixing pot and mixed evenly to obtain slurry A. Slurry A is poured into an energy storage sandwich mold 5 with a high thermal conductivity platform 1 at the bottom (structure as shown). Figure 1-3 As shown, after standing for 10 seconds, it is transferred to an ultra-low temperature medium for cryogenic casting and frozen for 24 hours until the block is completely solidified, resulting in solidified energy storage sandwich material B. Energy storage sandwich material B is placed in an environment of 0-4℃ and slowly thawed for 20 hours to obtain energy storage sandwich material C. Energy storage sandwich material C is placed in a cement curing box and cured for 28 days to obtain energy storage sandwich material D with a directional pore structure. Energy storage sandwich material D with a directional pore structure is immersed in a 2M zinc sulfate solution for 48 hours, then removed and allowed to stand for 3 hours to obtain energy storage sandwich material E with a directional pore structure, i.e., cement-based electrolyte. Vanadium oxide mesh electrodes and zinc mesh electrodes are immersed in liquid nitrogen for 30 seconds, then quickly spliced ​​with energy storage sandwich material E with a directional pore structure to obtain the assembled energy storage sandwich F.

[0086] 130 parts of silicate cement and 215 parts of filler were poured into a mixing pot and stirred at 130 rpm for 1 minute. 27 parts of water and 3.15 parts of water-reducing agent were mixed and added to a mixer, which was then stirred at 60 rpm for 3 minutes to obtain slurry G. A portion of slurry G was poured into a high-strength outer shell mold 7 (e.g., Figure 5 As shown in the diagram, the slurry G is aligned with the base 6 in the high-strength outer shell mold 7. The mold is placed on a concrete vibrating table and vibrated for 30 seconds. Then, the assembled energy storage core F is placed on the base 6 of the high-strength outer shell mold 7, and the remaining slurry G is poured in. The mold is then placed on a concrete vibrating table and vibrated for 50 seconds. After 28 days, a high-strength energy storage floor tile is obtained. The dimensions of the prepared high-strength energy storage floor tile are 300×300×15mm, and the dimensions of the energy storage core are 260×260×7mm. The dimensional diagram is shown in the diagram. Figure 6-7 As shown.

[0087] Example 2

[0088] A high-strength energy storage floor tile includes an energy storage core and a high-strength outer shell.

[0089] like Figure 4 As shown, the energy storage sandwich includes a cement-based electrolyte and positive and negative electrodes assembled on opposite sides of the cement-based electrolyte, and the high-strength outer shell is an ultra-high performance concrete-based outer shell.

[0090] The cement-based electrolyte comprises the following components in parts by weight:

[0091]

[0092] The ultra-high performance concrete shell comprises the following components in parts by weight:

[0093]

[0094] In this embodiment, the positive electrode is a vanadium oxide mesh electrode, and the negative electrode is a zinc mesh electrode.

[0095] In this embodiment, the cementitious material comprises the following components in parts by weight: 80% silicate cement, 10% fly ash, and 10% silica fume; the water-reducing agent is a polycarboxylate water-reducing agent, specifically a high-early-strength polycarboxylate water-reducing agent; the modifier is polyacrylamide (weight-average molecular weight of 10 million Daltons); the early-strength agent comprises the following components in parts by weight: 50% gypsum and 50% water glass, wherein the modulus of the water glass is 2.5. The filler comprises the following components in parts by weight: 20% silica fume, 72% quartz sand with a particle size of 0.4-1 mm, and 8% quartz powder with a particle size of 5-100 micrometers.

[0096] The preparation process of the high-strength energy storage floor brick is as follows: First, 70 parts of cementitious material, 0.18 parts of water-reducing agent, 5.25 parts of early-strength agent, and 20 parts of water are placed in a mixing pot and mixed evenly. Then, 0.11 parts of modifier are placed in the mixing pot and mixed evenly to obtain slurry A. Slurry A is poured into an energy storage sandwich mold 5 with a high thermal conductivity platform 1 at the bottom (structure as shown). Figure 1-3 As shown, after standing for 10 seconds, it is transferred to an ultra-low temperature medium for cryogenic casting and frozen for 24 hours until the block is completely solidified, resulting in solidified energy storage sandwich material B. Energy storage sandwich material B is placed in an environment of 0-4℃ and slowly thawed for 20 hours to obtain energy storage sandwich material C. Energy storage sandwich material C is placed in a cement curing box and cured for 28 days to obtain energy storage sandwich material D with a directional pore structure. Energy storage sandwich material D with a directional pore structure is immersed in a 2M zinc sulfate solution for 48 hours, then removed and allowed to stand for 3 hours to obtain energy storage sandwich material E with a directional pore structure, i.e., cement-based electrolyte. Vanadium oxide mesh electrodes and zinc mesh electrodes are immersed in liquid nitrogen for 30 seconds, then quickly spliced ​​with energy storage sandwich material E with a directional pore structure to obtain the assembled energy storage sandwich F.

[0097] 130 parts of silicate cement and 215 parts of filler were poured into a mixing pot and stirred at 130 rpm for 1 minute. 27 parts of water and 3.15 parts of water-reducing agent were mixed and added to a mixer, which was then stirred at 60 rpm for 3 minutes to obtain slurry G. A portion of slurry G was poured into a high-strength outer shell mold 7 (e.g., Figure 5As shown in the figure, the slurry G is aligned with the base 6 in the high-strength outer shell mold 7. The mold is placed on a concrete vibrating table and vibrated for 30 seconds. Then, the assembled energy storage core F is placed on the base 6 of the high-strength outer shell mold 7, and the remaining slurry G is poured in. The mold is placed on a concrete vibrating table and vibrated for 50 seconds. It is then placed in a standard concrete curing box. After 28 days, a high-strength energy storage floor tile is obtained. The dimensions of the high-strength energy storage floor tile are 300×300×15mm, and the dimensions of the energy storage core are 260×260×7mm.

[0098] Example 3

[0099] A high-strength energy storage floor tile includes an energy storage core and a high-strength outer shell.

[0100] like Figure 4 As shown, the energy storage sandwich includes a cement-based electrolyte and positive and negative electrodes assembled on opposite sides of the cement-based electrolyte, and the high-strength outer shell is an ultra-high performance concrete-based outer shell.

[0101] The cement-based electrolyte comprises the following components in parts by weight:

[0102]

[0103] The ultra-high performance concrete shell comprises the following components in parts by weight:

[0104]

[0105] In this embodiment, the positive electrode is a vanadium oxide mesh electrode, and the negative electrode is a zinc mesh electrode.

[0106] In this embodiment, the cementitious material comprises the following components in parts by weight: 80% silicate cement, 10% fly ash, and 10% silica fume; the water-reducing agent is a polycarboxylate water-reducing agent, specifically a high-early-strength polycarboxylate water-reducing agent; the modifier is polyacrylamide (weight-average molecular weight of 10 million Daltons); the early-strength agent comprises the following components in parts by weight: 50% gypsum and 50% water glass, wherein the modulus of the water glass is 2.5. The filler comprises the following components in parts by weight: 20% silica fume, 72% quartz sand with a particle size of 0.4-1 mm, and 8% quartz powder with a particle size of 5-100 micrometers.

[0107] The preparation process of the high-strength energy storage floor brick is as follows: First, 70 parts of cementitious material, 0.18 parts of water-reducing agent, 5.25 parts of early-strength agent, and 35 parts of water are placed in a mixing pot and mixed evenly. Then, 0.11 parts of modifier are placed in the mixing pot and mixed evenly to obtain slurry A. Slurry A is poured into an energy storage sandwich mold 5 with a high thermal conductivity platform 1 at the bottom (structure as shown). Figure 1-3As shown, after standing for 10 seconds, it is transferred to an ultra-low temperature medium for cryogenic casting and frozen for 24 hours until the block is completely solidified, resulting in solidified energy storage sandwich material B. Energy storage sandwich material B is placed in an environment of 0-4℃ and slowly thawed for 20 hours to obtain energy storage sandwich material C. Energy storage sandwich material C is placed in a cement curing box and cured for 28 days to obtain energy storage sandwich material D with a directional pore structure. Energy storage sandwich material D with a directional pore structure is immersed in a 2M zinc sulfate solution for 48 hours, then removed and allowed to stand for 3 hours to obtain energy storage sandwich material E with a directional pore structure, i.e., cement-based electrolyte. Vanadium oxide mesh electrodes and zinc mesh electrodes are immersed in liquid nitrogen for 30 seconds, then quickly spliced ​​with energy storage sandwich material E with a directional pore structure to obtain the assembled energy storage sandwich F.

[0108] 130 parts of silicate cement and 215 parts of filler were poured into a mixing pot and stirred at 130 rpm for 1 minute. 50 parts of water and 3.15 parts of water-reducing agent were mixed and added to a mixer, which was then stirred at 60 rpm for 3 minutes to obtain slurry G. A portion of slurry G was poured into a high-strength outer shell mold 7 (e.g., Figure 5 As shown in the figure, the slurry G is aligned with the base 6 in the high-strength outer shell mold 7. The mold is placed on a concrete vibrating table and vibrated for 30 seconds. Then, the assembled energy storage core F is placed on the base 6 of the high-strength outer shell mold 7, and the remaining slurry G is poured in. The mold is placed on a concrete vibrating table and vibrated for 50 seconds. It is then placed in a standard concrete curing box. After 28 days, a high-strength energy storage floor tile is obtained. The dimensions of the high-strength energy storage floor tile are 300×300×15mm, and the dimensions of the energy storage core are 260×260×7mm.

[0109] Comparative Example 1

[0110] A type of energy storage floor tile

[0111] The cement-based electrolyte comprises the following components in parts by weight:

[0112]

[0113]

[0114] In this comparative example, the positive electrode is a vanadium oxide mesh electrode, and the negative electrode is a zinc mesh electrode.

[0115] In this comparative example, the cementitious materials comprise the following components by weight: 80% silicate cement, 10% fly ash, and 10% silica fume; the water-reducing agent is a polycarboxylate water-reducing agent, specifically a high-early-strength polycarboxylate water-reducing agent; the modifier is polyacrylamide (weight-average molecular weight of 10 million Daltons); the early-strength agent comprises the following components by weight: 50% gypsum and 50% water glass, wherein the modulus of the water glass is 2.5. The filler comprises the following components by weight: 20% silica fume, 72% quartz sand with a particle size of 0.4-1 mm, and 8% quartz powder with a particle size of 5-100 micrometers.

[0116] The preparation process of the high-strength energy storage floor brick is as follows: First, 70 parts of cementitious material, 0.18 parts of water-reducing agent, 5.25 parts of early-strength agent, and 35 parts of water are placed in a mixing pot and mixed evenly. Then, 0.11 parts of modifier are placed in the mixing pot and mixed evenly to obtain slurry A. Slurry A is poured into an energy storage sandwich mold 5 with a high thermal conductivity platform 1 at the bottom (structure as shown). Figure 1-3 As shown, after standing for 10 seconds, it is transferred to an ultra-low temperature medium for cryogenic casting and frozen for 24 hours until the block is completely solidified, resulting in solidified energy storage sandwich material B. Energy storage sandwich material B is placed in an environment of 0-4℃ and slowly thawed for 20 hours to obtain energy storage sandwich material C. Energy storage sandwich material C is placed in a cement curing box and cured for 28 days to obtain energy storage sandwich material D with a directional pore structure. Energy storage sandwich material D with a directional pore structure is immersed in a 2M zinc sulfate solution for 48 hours, then removed and allowed to stand for 3 hours to obtain energy storage sandwich material E with a directional pore structure, i.e., cement-based electrolyte. Vanadium oxide mesh electrodes and zinc mesh electrodes are immersed in liquid nitrogen for 30 seconds, then quickly spliced ​​with energy storage sandwich material E with a directional pore structure to obtain energy storage floor tiles.

[0117] Comparative Example 2

[0118] A high-strength energy storage floor tile includes an energy storage core and a high-strength outer shell.

[0119] like Figure 4 As shown, the energy storage sandwich includes a cement-based electrolyte and positive and negative electrodes assembled on opposite sides of the cement-based electrolyte, and the high-strength outer shell is an ultra-high performance concrete-based outer shell.

[0120] The cement-based electrolyte comprises the following components in parts by weight:

[0121]

[0122] The ultra-high performance concrete shell comprises the following components in parts by weight:

[0123]

[0124] In this comparative example, the positive electrode is a vanadium oxide mesh electrode, and the negative electrode is a zinc mesh electrode.

[0125] In this comparative example, the cementitious materials comprise the following components by weight: 80% silicate cement, 10% fly ash, and 10% silica fume; the water-reducing agent is a polycarboxylate water-reducing agent, specifically a high-early-strength polycarboxylate water-reducing agent; the modifier is polyacrylamide (weight-average molecular weight of 10 million Daltons); the early-strength agent comprises the following components by weight: 50% gypsum and 50% water glass, wherein the modulus of the water glass is 2.5. The filler comprises the following components by weight: 20% silica fume, 72% quartz sand with a particle size of 0.4-1 mm, and 8% quartz powder with a particle size of 5-100 micrometers.

[0126] The preparation process of the high-strength energy storage floor brick is as follows: First, 70 parts of cementitious material, 0.18 parts of water-reducing agent, 5.25 parts of early-strength agent, and 35 parts of water are placed in a mixing pot and mixed evenly. Then, 0.11 parts of modifier are placed in the mixing pot and mixed evenly to obtain slurry A. Slurry A is poured into an energy storage sandwich mold 5 with a high thermal conductivity platform 1 at the bottom (structure as shown). Figure 1-3 As shown in the figure, after standing for 10 seconds, it is placed in a cement curing box and cured for 28 days to obtain energy storage sandwich material B with a directional pore structure. Energy storage sandwich material B is then immersed in a 2M zinc sulfate solution for 48 hours, removed, and left to stand for 3 hours to obtain energy storage sandwich material C, i.e., cement-based electrolyte. Vanadium oxide mesh electrodes and zinc mesh electrodes are immersed in liquid nitrogen for 30 seconds, removed, and quickly spliced ​​with energy storage sandwich material E with a directional pore structure to obtain the assembled energy storage sandwich D.

[0127] 130 parts of silicate cement and 215 parts of filler were poured into a mixing pot and stirred at 130 rpm for 1 minute. 27 parts of water and 3.15 parts of water-reducing agent were mixed and added to a mixer, which was then stirred at 60 rpm for 3 minutes to obtain slurry E. A portion of slurry G was poured into a high-strength outer shell mold 7 (e.g., Figure 5 As shown in the figure, the slurry E is aligned with the base 6 in the high-strength outer shell mold 7. The mold is placed on a concrete vibrating table and vibrated for 30 seconds. Then, the assembled energy storage core D is placed on the base 6 of the high-strength outer shell mold 7, and the remaining slurry E is poured in. The mold is placed on a concrete vibrating table and vibrated for 50 seconds. It is then placed in a standard concrete curing box. After 28 days, a high-strength energy storage floor tile is obtained. The dimensions of the high-strength energy storage floor tile are 300×300×15mm, and the dimensions of the energy storage core are 260×260×7mm.

[0128] Comparative Example 3

[0129] A high-strength energy storage floor tile includes an energy storage core and a high-strength outer shell.

[0130] like Figure 4 As shown, the energy storage sandwich includes a cement-based electrolyte and positive and negative electrodes assembled on opposite sides of the cement-based electrolyte, and the high-strength outer shell is an ultra-high performance concrete-based outer shell.

[0131] The cement-based electrolyte comprises the following components in parts by weight:

[0132]

[0133] The ultra-high performance concrete shell comprises the following components in parts by weight:

[0134]

[0135] In this comparative example, the positive electrode is a vanadium oxide sheet electrode, and the negative electrode is a zinc sheet electrode.

[0136] In this comparative example, the cementitious materials comprise the following components by weight: 80% silicate cement, 10% fly ash, and 10% silica fume; the water-reducing agent is a polycarboxylate water-reducing agent, specifically a high-early-strength polycarboxylate water-reducing agent; the modifier is polyacrylamide (weight-average molecular weight of 10 million Daltons); the early-strength agent comprises the following components by weight: 50% gypsum and 50% water glass, wherein the modulus of the water glass is 2.5. The filler comprises the following components by weight: 20% silica fume, 72% quartz sand with a particle size of 0.4-1 mm, and 8% quartz powder with a particle size of 5-100 micrometers.

[0137] The preparation process of the high-strength energy storage floor brick is as follows: First, 70 parts of cementitious material, 0.18 parts of water-reducing agent, 5.25 parts of early-strength agent, and 35 parts of water are placed in a mixing pot and mixed evenly. Then, 0.11 parts of modifier are placed in the mixing pot and mixed evenly to obtain slurry A. Slurry A is poured into a mold with a high thermal conductivity platform at the bottom, left to stand for 10 seconds, and then transferred to an ultra-low temperature medium for cryogenic casting. The block is frozen for 24 hours until it is completely solidified to obtain solidified energy storage sandwich material B. Energy storage sandwich material B is placed in an environment of 0-4℃ and slowly thawed for 20 hours to obtain energy storage sandwich material C. Energy storage sandwich material C is placed in a cement curing box and cured for 28 days to obtain energy storage sandwich material D with an oriented pore structure. Energy storage sandwich material D with an oriented pore structure is soaked in 2M zinc sulfate solution for 48 hours, removed, and left to stand for 3 hours to obtain energy storage sandwich material E with an oriented pore structure, i.e., cement-based electrolyte. Vanadium oxide sheet electrodes and zinc sheet electrodes are spliced ​​with an energy storage sandwich material E having a directional pore structure to obtain an assembled energy storage sandwich F.

[0138] 130 parts of silicate cement and 215 parts of filler were poured into a mixing pot and stirred at 130 rpm for 1 minute. 27 parts of water and 3.15 parts of water-reducing agent were mixed and added to a mixer, which was then stirred at 60 rpm for 3 minutes to obtain slurry G. A portion of slurry G was poured into a high-strength outer shell mold 7 (e.g., Figure 5 As shown in the figure, the slurry G is aligned with the base 6 in the high-strength outer shell mold 7. The mold is placed on a concrete vibrating table and vibrated for 30 seconds. Then, the assembled energy storage core F is placed on the base 6 of the high-strength outer shell mold 7, and the remaining slurry G is poured in. The mold is placed on a concrete vibrating table and vibrated for 50 seconds. It is then placed in a standard concrete curing box. After 28 days, a high-strength energy storage floor tile is obtained. The dimensions of the high-strength energy storage floor tile are 300×300×15mm, and the dimensions of the energy storage core are 260×260×7mm.

[0139] The compressive strength of the energy storage floor bricks prepared in Examples 1-3 and Comparative Examples 1-3 was tested according to the national standard "Test Method for Strength of Cement Mortar (ISO Method)" (GB / T17671-2021). A universal testing machine was used as the testing instrument. Electrochemical impedance spectroscopy was used to study the interfacial impedance, and the electrolyte ionic conductivity and the electrode-electrolyte cross-sectional impedance were obtained through fitting and calculation. At 25℃, 1 mA / cm²... 2 The coulombic efficiency of a cement-based zinc battery was tested after 10,000 cycles at a current density.

[0140] Table 1. Performance of cement-based zinc batteries prepared in Examples 1-3 and Comparative Examples 1-3

[0141]

[0142] As shown in Table 1, compared to Comparative Example 2, the cement-based electrolyte with a directional pore structure prepared by cryogenic casting technology in Examples 1-3 exhibits higher ionic conductivity; compared to Comparative Example 1, the energy storage tiles prepared by using ultra-high performance concrete as the outer shell in Examples 1-3 have higher compressive strength; compared to Comparative Example 3, the energy storage tiles prepared by using a mesh-like energy storage sandwich mold and mesh electrodes in Examples 1-3 have lower interfacial impedance; and compared to Comparative Examples 2 and 3, Examples 1-3 demonstrate superior stability. This is because Comparative Example 2 did not employ cryogenic casting, which significantly reduced the ion transport efficiency within its material. For Comparative Example 3, the lack of mesh electrodes affected the stability of its contact performance. Therefore, Examples 1-3 effectively improved their overall stability by employing cryogenic casting and mesh electrodes.

[0143] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A method for preparing high-strength energy storage floor tiles, characterized in that, The high-strength energy storage floor tile includes an energy storage core and a high-strength outer shell. The energy storage sandwich includes a cement-based electrolyte and positive and negative electrodes assembled on opposite sides of the cement-based electrolyte, and the high-strength outer shell is an ultra-high performance concrete-based outer shell. The cement-based electrolyte has a directionally arranged pore structure with a pore size of 10-20 μm and a porosity of 25-40%. The positive and negative electrodes are mesh electrodes; The length × width of the energy storage sandwich is (250-260) × (250-260) mm, and the vertical height is 5-7 mm. The length × width of the high-strength energy storage floor tile is (290-300) × (290-300) mm, and the vertical height is 13-15 mm. The orientation of the pores in the oriented pore structure is consistent with the vertical direction of the cement-based electrolyte, and the positive and negative electrodes are respectively disposed on both sides of the vertical direction of the cement-based electrolyte; The preparation method includes the following steps: S1: Mix the cementitious material, water-reducing agent, early strength agent and water until homogeneous, then add the modifier and mix until homogeneous to obtain slurry A; S2: Pour slurry A into the energy storage sandwich mold and let it stand; S3: Place the energy storage sandwich mold containing slurry A on an ultra-low temperature medium for cryogenic casting to obtain solidified energy storage sandwich material B; S4: Thaw the solidified energy storage sandwich material B to obtain energy storage sandwich material C. Then, place energy storage sandwich material C in a cement curing box and cure it for 20-32 days to obtain energy storage sandwich material D with directional pore structure. S5: Immerse the energy storage sandwich material D with a directional pore structure into the electrolyte solution to obtain the energy storage sandwich material E with a directional pore structure, i.e., the cement-based electrolyte. S6: Immerse the electrode material in liquid nitrogen solution for cooling and shrinkage, and then quickly splice the electrode with the energy storage sandwich material E with oriented pore structure to obtain the assembled energy storage sandwich F. S7: Mix silicate cement and filler in proportion, add water-reducing agent and water mixture, and mix again to obtain slurry G; S8: Place the energy storage sandwich into the high-strength outer shell mold, pour in the slurry G, so that the slurry G surrounds the energy storage sandwich, and cure it in the standard concrete curing box for 20-32 days to obtain the high-strength energy storage floor tile; In step S2, the energy storage sandwich mold includes a high thermal conductivity platform (1), a grid base (2) set on the high thermal conductivity platform (1), a low thermal conductivity frame (3) set around the grid base (2), and a low thermal conductivity grid cover plate (4) set on the low thermal conductivity frame (3). Only the high thermal conductivity platform (1) of the energy storage sandwich mold is in contact with the cryogenic medium.

2. The method for preparing a high-strength energy storage floor tile according to claim 1, characterized in that, The cement-based electrolyte comprises the following components in parts by weight: 50-90 parts of cementitious material; Water-reducing agent 0.14-0.22 parts; Modifier 0.08-0.15 parts; Early-strength agent: 4.75-5.75 parts; 17-35 parts water; The ultra-high performance concrete base shell comprises the following components in parts by weight: 100-150 parts of silicate cement; 180-250 parts of filler; Water-reducing agent: 2.75-3.55 parts; 27-50 parts water.

3. The method for preparing a high-strength energy storage floor tile according to claim 2, characterized in that, The cementitious material is selected from any one or more of silicate cement, fly ash, and silica fume; The water-reducing agent in the cement-based electrolyte and ultra-high performance concrete-based shell components is a polycarboxylate water-reducing agent. The modifier is polyacrylamide; The early strength agent is selected from any one or more of gypsum and water glass; The filler is selected from any one or more of silica fume, quartz sand, and quartz powder.

4. The method for preparing a high-strength energy storage floor tile according to claim 1, characterized in that, In step S5, the electrolyte solution is a zinc sulfate solution with a concentration of 1-2M. In step S6, the electrode material is a mesh electrode, which includes a positive electrode and a negative electrode. The positive electrode is a vanadium oxide mesh electrode, and the negative electrode is a zinc mesh electrode. The electrode material is immersed in liquid nitrogen solution for 20-40 seconds to shrink.

5. The method for preparing a high-strength energy storage floor tile according to claim 1, characterized in that, Step S8 includes the following steps: S8.1: Pour 35~50 wt% of slurry G into the high-strength shell mold. The height of the poured slurry G should be flush with the base in the high-strength shell mold. S8.2: Place the assembled energy storage sandwich F on the base in the high-strength outer shell mold, pour in the remaining slurry G, so that the slurry G surrounds the energy storage sandwich, and cure it in a standard concrete curing box for 20-32 days to obtain the high-strength energy storage floor tile.

6. The method for preparing a high-strength energy storage floor tile according to claim 5, characterized in that, In step S8.1, after pouring in the 35~50 wt% slurry G, the high-strength outer shell mold needs to be placed on a concrete vibration table and vibrated for 20-40 seconds. In step S8.2, after pouring in the remaining slurry G, the high-strength outer shell mold needs to be placed on a concrete vibration table and vibrated for 40-60 seconds. The entire process of step S8 takes no more than 5 minutes to complete.

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