Cement-based zinc battery with low interfacial impedance and preparation method and application thereof

Abstract

This invention relates to a low interfacial impedance cement-based zinc battery, its preparation method, and its application. The cement-based zinc battery includes a cement-based electrolyte, and positive and negative electrode material layers on opposite sides of the surface of the cement-based electrolyte are respectively fused using 3D printing technology. The specific steps are as follows: a porous cement-based structure is manufactured using cryogenic casting technology and then used after salt solution immersion treatment; the cement-based electrolyte and zinc (copper) electrodes are assembled in an inert gas-filled environment using a fixed laser scanner and 3D printing equipment, with copper as the positive electrode, the cement-based structure as the electrolyte, and zinc as the negative electrode. Compared with existing technologies, this invention directly fuses the electrode material onto the surface of the cement-based electrolyte, improving the interfacial stability between the electrode and the electrolyte, solving the problem of high interfacial impedance between the electrolyte and the electrode, improving the overall battery performance, and the process is simple.

Description

Technical Field

[0001] This invention relates to the field of electrochemical energy storage technology, and in particular to a cement-based zinc battery with low interfacial impedance, its preparation method, and its application. Background Technology

[0002] With the continuous development of sustainable energy technologies, cement-based batteries, as an innovative energy storage solution, have attracted increasing attention. Cement-based batteries possess excellent mechanical properties and the ability to convert electrical energy into chemical energy, making them suitable as building components while alleviating reliance on traditional energy storage devices. However, the interfacial stability between the cement-based electrolyte and the electrode is one of the key technologies limiting its widespread application. Poor solid-solid contact between the electrode and electrolyte in cement-based batteries leads to significant interfacial impedance and restricts interfacial ion transport, affecting battery life and overall performance. Traditional research typically improves the interfacial stability between the cement-based electrolyte and the electrode through ion doping-induced interface modification, various types of surface coatings and interlayers, external pressure, and increasing the operating temperature. Specific examples include applying wetting agents; adding polymer interfacial layers; adding alloy interlayers; adding quasi-solid organic interlayers; adding soft and ion-conducting interlayer materials; applying external pressure to ensure tight contact between the electrode and electrolyte; and increasing the operating temperature of the cement-based battery. However, its disadvantages are also quite obvious: insufficient stability of chemical modification; capacity reduction due to slight volatilization or decomposition of organic liquid electrolyte during cycling; controversy over battery safety due to the addition of polymers; poor conductivity of intermediate layer material; and material damage caused by pressure.

[0003] Therefore, improving the contact stability between the electrode and the electrolyte without causing significant side effects has become a current research hotspot. Summary of the Invention

[0004] The purpose of this invention is to provide a cement-based zinc battery with low interfacial impedance, its preparation method and application, to improve the interfacial stability of the electrolyte and electrode of the cement-based battery, reduce the interfacial impedance without producing significant side effects.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] On one hand, the present invention provides a cement-based zinc battery with low interfacial impedance, the cement-based zinc battery comprising a cement-based electrolyte, and positive electrode material layers and negative electrode material layers respectively fused to opposite sides of the surface of the cement-based electrolyte by 3D printing technology.

[0007] Preferably, the vertical height of the cement-based electrolyte is 15-20 mm, and the cement-based electrolyte has an oriented pore structure with a pore size of 10-20 μm and a porosity of 20-40%.

[0008] Preferably, the orientation of the oriented pore structure is consistent with the vertical direction of the cement-based electrolyte, and the positive electrode material layer and the negative electrode material layer are respectively fused to both sides of the cement-based electrolyte in the vertical direction.

[0009] In this invention, positive and negative electrode material layers are printed on both sides of the cement-based electrolyte in the vertical direction using 3D printing technology, allowing liquid metal to penetrate into the porous structure of the cement-based electrolyte surface layer. This significantly improves the adhesion strength between the cement-based electrolyte and the metal electrode, reducing the possibility of separation at the interface under working conditions.

[0010] Preferably, the positive electrode material layer is copper with a thickness of 2-3 mm.

[0011] Preferably, the negative electrode material layer is zinc and has a thickness of 2-3 mm.

[0012] Preferably, the low interfacial impedance cement-based zinc battery comprises the following components in parts by mass:

[0013]

[0014] More preferably, the low interfacial impedance cement-based zinc battery comprises the following components in parts by mass:

[0015]

[0016] More preferably, the cementing material is selected from any one or more of silicate cement, fly ash, and silica fume.

[0017] More preferably, the water-reducing agent is selected from any one or more of polycarboxylate water-reducing agents and lignin sulfonates.

[0018] More preferably, the modifier is selected from any one or more of polyacrylamide and bentonite.

[0019] More preferably, the early strength agent is selected from any one or more of gypsum and water glass.

[0020] More preferably, the zinc powder has a particle size range of 45-150 μm.

[0021] More preferably, the copper powder has a particle size range of 45-150 μm.

[0022] Secondly, the present invention also provides a method for preparing the above-mentioned low interfacial impedance cement-based zinc battery, comprising the following preparation steps:

[0023] S1. Immerse cement-based material D in zinc sulfate solution to obtain cement-based material E;

[0024] S2. Remove impurities from the surface of cement-based material E. After cleaning the surface, cement-based material F, i.e., cement-based electrolyte, is obtained.

[0025] S3. Use a fixed laser scanner to scan and model the surface of cement-based material F, and input the obtained model data into a coaxial powder feeding 3D printer.

[0026] S4. In an inert gas environment, zinc electrode material layers and copper electrode material layers are printed on opposite sides of cement-based material F using a coaxial powder feeding 3D printer to obtain the cement-based zinc battery with low interfacial impedance.

[0027] Preferably, in step S4, the inert gas environment includes an argon environment.

[0028] Preferably, in step S4, after the zinc electrode material layer is printed, it is allowed to stand and cool for 2-4 hours. Then, the cement-based material F is flipped over, and the copper electrode material layer is printed on the opposite side. After the copper electrode material layer is printed, it is allowed to stand and cool for another 2-4 hours.

[0029] Preferably, in step S4, the 3D printing parameters are: printing speed 5-10 mm / s, printing height 2-3 mm, and printing time 60-80 min.

[0030] Preferably, in step S3, the model data needs to be processed and converted before being input into the coaxial toner-feeding 3D printer.

[0031] Preferably, in step S2, a hard brush is used to remove impurities from the surface of the cement-based material E. The surface impurities are mainly the surface passivation layer and particles with poor adhesion.

[0032] Preferably, in step S1, the concentration of the zinc sulfate solution is 1-2M, and the immersion time is 24-48h.

[0033] Preferably, in step S1, the immersion time is related to the vertical height of the cement-based material D.

[0034] More preferably, in step S1, cement-based material D with a vertical height of 15 mm needs to be immersed for 24 hours, and cement-based material D with a vertical height of 20 mm needs to be immersed for 48 hours. After being taken out, it is left to stand for 3 hours, and then the surface liquid is wiped dry.

[0035] Preferably, in step S1, the cement-based material is prepared through the following steps:

[0036] S1.1 Mix the cementitious material, water-reducing agent, early strength agent and water according to the mass fractions and stir evenly. Then add the modifier and mix evenly to obtain slurry A.

[0037] S1.2 Pour slurry A into a mold with a heat-conducting plate at the bottom and let it stand;

[0038] S1.3 Place the mold containing slurry A on an ultra-low temperature medium for cryogenic casting to quickly obtain solidified cement slurry B;

[0039] S1.4 Thaw the solidified cement paste B to obtain block C, and then place block C in a cement curing box for 24-30 days to obtain cement-based material D with a directional pore structure.

[0040] More preferably, in step S1.1, the mixing speed of the cementitious material, water-reducing agent, early-strength agent and water is 60±5 r / min.

[0041] More preferably, in step S1.1, the rotation speed for mixing and stirring after adding the modifier is 130±10 r / min.

[0042] More preferably, in step S1.2, the settling time is 8-15 seconds.

[0043] More preferably, in step S1.3, the cryogenic medium includes liquid nitrogen.

[0044] More preferably, in step S1.3, only the bottom heat-conducting template of the mold is in contact with the liquid nitrogen.

[0045] More preferably, in step S1.4, the thawing process involves placing the sample in a constant temperature environment of 0-4℃ for slow thawing, with a thawing time of 24-30 hours.

[0046] More preferably, in step S1.4, when the vertical height of the block C is 15 mm, it needs to be cured for 24 hours.

[0047] More preferably, in step S1.4, when the vertical height of the block C is 20 mm, it needs to be cured for 30 hours.

[0048] Traditional research has improved the interfacial stability of cement-based electrolytes and electrodes through methods such as ion doping, surface coating, pressurization, and heating. However, these methods also have significant side effects, including poor chemical stability, wetting agent volatilization, polymer safety controversies, poor conductivity of the intermediate layer, and pressure damage. This invention, in its preparation process, does not use additional chemical modifications or wetting agents, nor does it add any additional surface coatings or intermediate layers, thus reducing the possibility of side effects to some extent.

[0049] Thirdly, the present invention also provides an application of the above-mentioned low interfacial impedance cement-based zinc battery in building components:

[0050] In wall components, low-interfacial-resistance cement-based zinc batteries are embedded in building walls to form load-bearing walls with energy storage capabilities. This provides the building with the necessary energy storage and stable power supply, while reducing the space requirements of independent battery energy storage systems. In floors and slabs, cement-based zinc battery modules are embedded, not only supporting the building load but also providing power support. In rooftop solar systems, cement-based zinc batteries are integrated with rooftop solar panels, making the battery modules an integral part of the roof structure. These modules are then used as energy storage modules for roof load-bearing supports or insulation panels, storing solar energy and providing a day-and-night energy supply for the building.

[0051] Compared with the prior art, the present invention has the following beneficial effects:

[0052] (1) By 3D printing electrodes on the surface of cement-based materials, the present invention can increase the contact area between cement-based materials and metal electrodes, significantly reduce the contact resistance between the electrode and electrolyte interface, and ensure the long-term stability of the electrode during use.

[0053] (2) This invention uses 3D printing technology to allow liquid metal to enter the micro-slits on the solid surface, which greatly improves the adhesion strength between the cement-based electrolyte and the metal electrode and reduces the possibility of separation at the interface under working conditions.

[0054] (3) This invention directly 3D prints electrodes on cement-based materials, eliminating the traditional electrode cutting and processing steps. The preparation process is simple, reducing material waste and energy consumption, and reducing waste generation, thus having good environmental benefits.

[0055] (4) No additional wetting agent or additional surface coatings and intermediate layers are used in the preparation process of this invention. Therefore, the cement-based zinc battery prepared by this invention overcomes the defects of poor stability, easy volatile electrolyte, low battery safety and conductivity to a certain extent compared with the prior art.

[0056] (5) The present invention provides a cement-based zinc battery with low interfacial impedance, which can be applied to building structures and alleviate the dependence on traditional energy storage equipment. Attached Figure Description

[0057] Figure 1 This is a 3D printing schematic diagram of the lateral path of the cement-based zinc battery with low interfacial impedance according to the present invention.

[0058] Figure 2 This is a schematic diagram of the 3D printing route for the lateral path of the low interfacial impedance cement-based zinc battery of the present invention.

[0059] In the figure, a-directionally arranged pore structure; b-cement-based electrolyte; 1-fixture; 2-3D printer; 3-laser; 4-metal electrode powder flow. Detailed Implementation

[0060] 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.

[0061] 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 and comparative examples are all commercially available.

[0062] Example 1

[0063] This embodiment provides a cement-based zinc battery with low interfacial impedance, comprising the following components in parts by mass:

[0064]

[0065] In this embodiment, the cementitious material comprises the following percentage components: 80% silicate cement, 10% fly ash, and 10% silica fume.

[0066] The water-reducing agent is a polycarboxylate water-reducing agent, specifically a high early strength polycarboxylate water-reducing agent.

[0067] The modifier comprises the following components by mass percentage: 60% polyacrylamide and 40% bentonite, wherein the weight-average molecular weight of the polyacrylamide is 10 million Daltons.

[0068] The early strength agent comprises the following components by mass percentage: 50% gypsum and 50% water glass, wherein the modulus of the water glass is 2.5.

[0069] The aforementioned low interfacial impedance cement-based zinc battery was prepared by the following steps:

[0070] First, 200 parts of cementitious material, 0.4 parts of water-reducing agent, 15 parts of early-strength agent, and 100 parts of water are placed in a mixing pot and mixed evenly. Then, 0.3 parts of modifier are added to the mixing pot and mixed evenly to obtain slurry A. Slurry A is poured into a mold with a heat-conducting template at the bottom and transferred to an ultra-low temperature medium for cryogenic casting. It is frozen for 24 hours until the block is completely solidified to obtain solidified cement slurry B. Cement slurry B is placed in an environment of 0-4℃ for slow thawing for 30 hours to obtain block C. Block C is placed in a cement curing box for curing for 28 days to obtain cement-based material D with a directional pore structure. Cement-based material D is soaked in 2M zinc sulfate solution for 48 hours, removed, and allowed to stand for 3 hours to obtain cement-based material E.

[0071] After wiping the liquid off the surface of cement-based material E, use a steel brush to remove the passivation layer and impurities from the surface of cement-based material E, obtaining cement-based material F. For example... Figure 1 and 2 As shown, a fixed laser scanner was used to scan and model the surface of cement-based material F. The model data was processed and converted before being input into a coaxial powder-feeding 3D printer. 2.5 parts zinc powder and 3 parts copper powder were added to the 3D printer's hopper. The cement-based material F and the 3D printer were placed in an argon atmosphere for printing. The 3D printer used had a laser power of 2KW and a printing speed of 5mm / s. In the argon-protected environment, the 3D printer was started, ensuring the oxygen content in the printing area was controlled below 50ppm to prevent metal oxidation. The control system activated the printing program based on the imported model data. Initial printing started from the center of the cement-based material F surface and proceeded along a rectangular circumferential path (e.g., ...). Figure 2 (As shown). The printing nozzle adjusts its height according to the modeling data, with the initial distance 0.1mm above the highest point on the surface. Due to the different heights at each position, the amount of powder output varies accordingly, ultimately achieving a smooth first layer of metal covering the surface. Subsequent layer-by-layer printing is then performed to form an actual working electrode thickness of 2-3mm. After printing the zinc electrode, it is allowed to cool for 3 hours, then flipped over, and the copper electrode printing begins. After the copper electrode printing is complete, it is cooled and allowed to stand for another 3 hours. Finally, it is removed from the argon atmosphere, yielding a cement-based zinc battery with low interfacial impedance.

[0072] Example 2

[0073] This embodiment provides a cement-based zinc battery with low interfacial impedance, comprising the following components in parts by mass:

[0074]

[0075] In this embodiment, the cementitious material comprises the following components by mass percentage: 80% silicate cement, 10% fly ash, and 10% silica fume.

[0076] The water-reducing agent is a polycarboxylate water-reducing agent, specifically a high early strength polycarboxylate water-reducing agent.

[0077] The modifier comprises the following components by mass percentage: 60% polyacrylamide and 40% bentonite, wherein the weight-average molecular weight of the polyacrylamide is 10 million Daltons.

[0078] The early strength agent comprises the following components by mass percentage: 50% gypsum and 50% water glass, wherein the modulus of the water glass is 2.5.

[0079] The aforementioned low interfacial impedance cement-based zinc battery was prepared by the following steps:

[0080] First, 200 parts of cementitious material, 0.4 parts of water-reducing agent, 15 parts of early-strength agent, and 80 parts of water are placed in a mixing pot and mixed evenly. Then, 0.3 parts of modifier are added to the mixing pot and mixed evenly to obtain slurry A. Slurry A is poured into a mold with a heat-conducting template at the bottom and transferred to an ultra-low temperature medium for cryogenic casting. It is frozen for 24 hours until the block is completely solidified to obtain solidified cement slurry B. Cement slurry B is placed in an environment of 0-4℃ for slow thawing for 30 hours to obtain block C. Block C is placed in a cement curing box for curing for 28 days to obtain cement-based material D with a directional pore structure. Cement-based material D is soaked in 2M zinc sulfate solution for 48 hours, removed, and allowed to stand for 3 hours to obtain cement-based material E.

[0081] After wiping the liquid off the surface of cement-based material E, use a steel brush to remove the passivation layer and impurities from the surface of cement-based material E, obtaining cement-based material F. For example... Figure 1 and 2 As shown, a fixed laser scanner was used to scan and model the surface of cement-based material F. The model data was processed and converted before being input into a coaxial powder-feeding 3D printer. 2.5 parts zinc powder and 3 parts copper powder were added to the 3D printer's hopper. The cement-based material F and the 3D printer were placed in an argon atmosphere for printing. The 3D printer used had a laser power of 2KW and a printing speed of 5mm / s. In the argon-protected environment, the 3D printer was started, ensuring the oxygen content in the printing area was controlled below 50ppm to prevent metal oxidation. The control system activated the printing program based on the imported model data. Initial printing started from the center of the cement-based material F surface and proceeded along a rectangular circumferential path (e.g., ...). Figure 2 (As shown). The printing nozzle adjusts its height according to the modeling data, with the initial distance 0.1mm above the highest point on the surface. Due to the different heights at each position, the amount of powder output varies accordingly, ultimately achieving a smooth first layer of metal covering the surface. Subsequent layer-by-layer printing is then performed to form an actual working electrode thickness of 2-3mm. After printing the zinc electrode, it is allowed to cool for 3 hours, then flipped over, and the copper electrode printing begins. After the copper electrode printing is complete, it is cooled and allowed to stand for another 3 hours. Finally, it is removed from the argon atmosphere, yielding a cement-based zinc battery with low interfacial impedance.

[0082] Example 3

[0083] This embodiment provides a cement-based zinc battery with low interfacial impedance, comprising the following components in parts by mass:

[0084]

[0085] In this embodiment, the cementitious material comprises the following components by mass percentage: 80% silicate cement, 10% fly ash, and 10% silica fume.

[0086] The water-reducing agent is a polycarboxylate water-reducing agent, specifically a high early strength polycarboxylate water-reducing agent.

[0087] The modifier comprises the following components by mass percentage: 60% polyacrylamide and 40% bentonite, wherein the weight-average molecular weight of the polyacrylamide is 10 million Daltons.

[0088] The early strength agent comprises the following components by mass percentage: 50% gypsum and 50% water glass, wherein the modulus of the water glass is 2.5.

[0089] The aforementioned low interfacial impedance cement-based zinc battery was prepared by the following steps:

[0090] First, 200 parts of cementitious material, 0.4 parts of water-reducing agent, 15 parts of early-strength agent, and 120 parts of water are placed in a mixing pot and mixed evenly. Then, 0.3 parts of modifier are added to the mixing pot and mixed evenly to obtain slurry A. Slurry A is poured into a mold with a heat-conducting template at the bottom and transferred to an ultra-low temperature medium for cryogenic casting. It is frozen for 24 hours until the block is completely solidified to obtain solidified cement slurry B. Cement slurry B is placed in an environment of 0-4℃ for slow thawing for 30 hours to obtain block C. Block C is placed in a cement curing box for curing for 28 days to obtain cement-based material D with a directional pore structure. Cement-based material D is soaked in 2M zinc sulfate solution for 48 hours, removed, and allowed to stand for 3 hours to obtain cement-based material E.

[0091] After wiping the liquid off the surface of cement-based material E, use a steel brush to remove the passivation layer and impurities from the surface of cement-based material E, obtaining cement-based material F. For example... Figure 1 and 2 As shown, a fixed laser scanner was used to scan and model the surface of cement-based material F. The model data was processed and converted before being input into a coaxial powder-feeding 3D printer. 2.5 parts zinc powder and 3 parts copper powder were added to the 3D printer's hopper. The cement-based material F and the 3D printer were placed in an argon atmosphere for printing. The 3D printer used had a laser power of 2KW and a printing speed of 5mm / s. In the argon-protected environment, the 3D printer was started, ensuring the oxygen content in the printing area was controlled below 50ppm to prevent metal oxidation. The control system activated the printing program based on the imported model data. Initial printing started from the center of the cement-based material F surface and proceeded along a rectangular circumferential path (e.g., ...). Figure 2(As shown). The printing nozzle adjusts its height according to the modeling data, with the initial distance 0.1mm above the highest point on the surface. Due to the different heights at each position, the amount of powder output varies accordingly, ultimately achieving a smooth first layer of metal covering the surface. Subsequent layer-by-layer printing is then performed to form an actual working electrode thickness of 2-3mm. After printing the zinc electrode, it is allowed to cool for 3 hours, then flipped over, and the copper electrode printing begins. After the copper electrode printing is complete, it is cooled and allowed to stand for another 3 hours. Finally, it is removed from the argon atmosphere, yielding a cement-based zinc battery with low interfacial impedance.

[0092] Comparative Example 1

[0093] This comparative example provides a cement-based zinc battery comprising the following components in parts by mass:

[0094]

[0095]

[0096] In this comparative example, the cementitious materials consist of the following components by mass percentage: 80% silicate cement, 10% fly ash, and 10% silica fume.

[0097] The water-reducing agent is a polycarboxylate water-reducing agent, specifically a high early strength polycarboxylate water-reducing agent.

[0098] The modifier comprises the following components by mass percentage: 60% polyacrylamide and 40% bentonite, wherein the weight-average molecular weight of the polyacrylamide is 10 million Daltons.

[0099] The early strength agent comprises the following components by mass percentage: 50% gypsum and 50% water glass, wherein the modulus of the water glass is 2.5.

[0100] The above-mentioned cement-based zinc battery is prepared by the following steps:

[0101] First, 200 parts of cementitious material, 0.4 parts of water-reducing agent, 15 parts of early-strength agent, and 100 parts of water are placed in a mixing pot and mixed evenly. Then, 0.3 parts of modifier are added to the mixing pot and mixed evenly to obtain slurry A. Slurry A is poured into a mold with a heat-conducting template at the bottom to obtain block B. Block B is placed in a cement curing box and cured for 28 days to obtain cement-based material C. Cement-based material C is soaked in a 2M zinc sulfate solution for 48 hours, then removed and allowed to stand for 3 hours to obtain cement-based material D.

[0102] After wiping the liquid off the surface of cement-based material D, use a steel brush to remove the passivation layer and impurities from the surface of cement-based material E, thus obtaining cement-based material E. For example... Figure 1As shown, a fixed laser scanner was used to scan and model the surface of cement-based material E. The model data was processed and converted before being input into a coaxial powder-feeding 3D printer. 2.5 parts zinc powder and 3 parts copper powder were added to the printer's hopper. The cement-based material E and the 3D printer were placed in an argon atmosphere for printing. The 3D printer used had a laser power of 2KW and a printing speed of 5mm / s. In the argon-protected environment, the 3D printer was started, ensuring the oxygen content in the printing area was controlled below 50ppm to prevent metal oxidation. The control system activated the printing program based on the imported model data. Initial printing started from the center of the sample, proceeding along a rectangular path. The print head adjusted its height according to the modeling data, starting 0.1mm above the highest point on the surface. Due to the different heights at various locations, the powder output varied accordingly, ultimately achieving a smooth first layer of metal covering the surface. Subsequent layer-by-layer printing was then performed to form an actual working electrode thickness of 2-3mm. After the zinc electrode is printed, it is left to cool for 3 hours, then flipped over and the copper electrode is printed. After the copper electrode is printed, it is cooled and left to stand for another 3 hours. Finally, it is taken out of the argon environment to obtain the cement-based zinc battery.

[0103] Comparative Example 2

[0104] This comparative example provides a cement-based zinc battery comprising the following components in parts by mass:

[0105]

[0106] In this comparative example, the cementitious materials consist of the following components by mass percentage: 80% silicate cement, 10% fly ash, and 10% silica fume.

[0107] The water-reducing agent is a polycarboxylate water-reducing agent, specifically a high early strength polycarboxylate water-reducing agent.

[0108] The modifier comprises the following components by mass percentage: 60% polyacrylamide and 40% bentonite, wherein the weight-average molecular weight of the polyacrylamide is 10 million Daltons.

[0109] The early strength agent comprises the following components by mass percentage: 50% gypsum and 50% water glass, wherein the modulus of the water glass is 2.5.

[0110] The above-mentioned cement-based zinc battery is prepared through the following steps:

[0111] First, 200 parts of cementitious material, 0.4 parts of water-reducing agent, 15 parts of early-strength agent, and 100 parts of water are placed in a mixing pot and mixed evenly. Then, 0.3 parts of modifier are added to the mixing pot and mixed evenly to obtain slurry A. Slurry A is poured into a mold with a heat-conducting template at the bottom and transferred to an ultra-low temperature medium for cryogenic casting. It is frozen for 24 hours until the block is completely solidified to obtain solidified cement slurry B. Cement slurry B is placed in an environment of 0-4℃ for slow thawing for 30 hours to obtain block C. Block C is placed in a cement curing box for curing for 28 days to obtain cement-based material D with a directional pore structure. Cement-based material D is soaked in 2M zinc sulfate solution for 48 hours, removed, and allowed to stand for 3 hours to obtain cement-based material E.

[0112] After wiping the liquid off the surface of cement-based material E, use a steel brush to remove the passivation layer and impurities from the surface of cement-based material E to obtain cement-based material F. Press a 3mm thick zinc sheet and a 3mm thick copper sheet onto both sides of cement-based material E at a pressure of 1.5MPa to obtain a cement-based zinc battery.

[0113] Comparative Example 3

[0114] This comparative example provides a cement-based zinc battery comprising the following components in parts by mass:

[0115]

[0116]

[0117] In this comparative example, the cementitious materials consist of the following components by mass percentage: 80% silicate cement, 10% fly ash, and 10% silica fume.

[0118] The water-reducing agent is a polycarboxylate water-reducing agent, specifically a high early strength polycarboxylate water-reducing agent.

[0119] The modifier comprises the following components by mass percentage: 60% polyacrylamide and 40% bentonite, wherein the weight-average molecular weight of the polyacrylamide is 10 million Daltons.

[0120] The early strength agent comprises the following components by mass percentage: 50% gypsum and 50% water glass, wherein the modulus of the water glass is 2.5.

[0121] The above-mentioned cement-based zinc battery is prepared through the following steps:

[0122] First, 200 parts of cementitious material, 0.4 parts of water-reducing agent, 15 parts of early-strength agent, and 100 parts of water are placed in a mixing pot and mixed evenly. Then, 0.3 parts of modifier are added to the mixing pot and mixed evenly to obtain slurry A. Slurry A is poured into a mold with a heat-conducting template at the bottom and transferred to an ultra-low temperature medium for cryogenic casting. It is frozen for 24 hours until the block is completely solidified to obtain solidified cement slurry B. Cement slurry B is placed in an environment of 0-4℃ for slow thawing for 30 hours to obtain block C. Block C is placed in a cement curing box for curing for 28 days to obtain cement-based material D with a directional pore structure. Cement-based material D is soaked in 2M zinc sulfate solution for 48 hours, removed, and allowed to stand for 3 hours to obtain cement-based material E.

[0123] After wiping the liquid off the surface of cement-based material E, the passivation layer and impurities on the surface of cement-based material E are removed with a steel brush to obtain cement-based material F. 2.5 parts zinc powder and 3 parts copper powder are placed in a tubular muffle furnace filled with argon gas. The zinc powder is heated to 500℃ to melt, and the copper powder is heated to 1200℃ to melt. In an argon-filled glove box, the molten zinc or copper is directly poured onto the surface of cement-based material E. After the zinc electrode is poured, it is allowed to cool for 3 hours, then turned over, and the copper electrode is poured. After the copper electrode is poured, it is cooled and allowed to stand for another 3 hours. Finally, it is removed from the argon environment to obtain a cement-based zinc battery.

[0124] The compressive strength of cement-based electrolyte samples (40mm × 40mm × 160mm) prepared in Examples 1-3 and Comparative Examples 1-3 was tested using a universal testing machine, in accordance with the national standard "Test Method for Strength of Cement Mortar (ISO Method)" (GB / T17671-2021). Electrochemical impedance spectroscopy was used to study the interfacial impedance, and the electrolyte ionic conductivity and electrode-electrolyte cross-sectional impedance were obtained through fitting and calculation. At 25℃, the resistance was 1 mA / cm². 2 The coulombic efficiency of a cement-based zinc battery was tested after 10,000 cycles at a current density.

[0125] Table 1. Performance of cement-based zinc batteries prepared in Examples 1-3 and Comparative Examples 1-3

[0126]

[0127] As can be seen from Table 1, compared with Comparative Example 1, the cement-based electrolyte with directional pore structure obtained by cryogenic casting technology in Example 1 of the present invention has a higher ionic conductivity. Furthermore, the use of 3D printing technology to print electrodes on the surface of the cement-based electrolyte greatly improves the interfacial impedance between the electrolyte and the electrode. At the same time, since 3D printing technology allows liquid metal electrode material to directly enter the micro-slits on the surface of the cement-based electrolyte, the adhesion strength between the cement-based electrolyte and the metal electrode is greatly improved, thereby reducing the possibility of separation at the interface under working conditions. Therefore, compared with Comparative Examples 1, 2, and 3, Examples 1-3 can still maintain a coulombic efficiency of 90% or above after 10,000 cycles, demonstrating good stability.

[0128] In summary, the cement-based zinc battery prepared by this invention has low interfacial impedance and long-term stability during use, which improves the overall performance of the battery. It can be applied to building structures and alleviate the dependence on traditional energy storage devices.

[0129] 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 cement-based zinc battery with low interfacial impedance, characterized in that, The cement-based zinc battery includes a cement-based electrolyte, with positive and negative electrode material layers respectively fused onto opposite sides of the surface of the cement-based electrolyte using 3D printing technology; the vertical height of the cement-based electrolyte is 15-20 mm, and the cement-based electrolyte has an oriented pore structure with a pore size of 10-20 μm and a porosity of 25-40%. Liquid metal penetrates into the porous structure of the cement-based electrolyte surface, which greatly improves the adhesion strength between the cement-based electrolyte and the metal electrode, reducing the possibility of separation at the interface under working conditions. The method for preparing the cement-based zinc battery includes the following preparation steps: S1. Immerse cement-based material D in zinc sulfate solution to obtain cement-based material E; S2. Remove impurities from the surface of cement-based material E, and after cleaning the surface, obtain the cement-based electrolyte; S3. Use a fixed laser scanner to scan and model the surface of the cement-based electrolyte, and input the obtained model data into a coaxial powder feeding 3D printer. S4. In an inert gas environment, zinc electrode material layers and copper electrode material layers are printed on opposite sides of the cement-based electrolyte using a coaxial powder feeding 3D printer to obtain the cement-based zinc battery with low interfacial impedance. In step S4, The inert gas environment includes an argon environment; After the zinc electrode material layer is printed, let it stand and cool for 2-4 hours. Then, flip the cement-based electrolyte and start printing the copper electrode material layer on the opposite side. After the copper electrode material layer is printed, let it stand and cool for 2-4 hours again. The 3D printing parameters are: printing speed 5-10 mm / s, printing height 2-3 mm, and printing time 60-80 min.

2. The low interfacial impedance cement-based zinc battery according to claim 1, characterized in that, The orientation of the pores in the oriented pore structure is consistent with the vertical direction of the cement-based electrolyte. The positive electrode material layer and the negative electrode material layer are respectively fused to both sides of the vertical direction of the cement-based electrolyte. The positive electrode material layer is copper with a thickness of 2-3 mm; the negative electrode material layer is zinc with a thickness of 2-3 mm.

3. The low interfacial impedance cement-based zinc battery according to claim 1, characterized in that, The components include the following parts by mass: 175-250 parts of cementitious material; Water-reducing agent: 0.2-0.6 parts; Modifier 0.1-0.5 parts; Early-strength agent 10-20 parts; 2-2.5 parts zinc powder; Copper powder 2.5-3 parts; 80-120 parts water.

4. A cement-based zinc battery with low interfacial impedance according to claim 3, 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 is selected from any one or more of polycarboxylate water-reducing agents and lignin sulfonates; The modifier is selected from any one or more of polyacrylamide and bentonite; The early strength agent is selected from any one or more of gypsum and water glass; The zinc powder has a particle size range of 45-150 μm; The copper powder has a particle size range of 45-150 μm.

5. A cement-based zinc battery with low interfacial impedance according to claim 1, characterized in that, In step S1, the concentration of the zinc sulfate solution is 1-2 M, and the immersion time is 24-48 h.

6. A cement-based zinc battery with low interfacial impedance according to claim 1, characterized in that, In step S1, the cement-based material D is prepared through the following steps: S1.1 Mix the cementitious material, water-reducing agent, early strength agent and water according to the mass fractions and stir evenly. Then add the modifier and mix evenly to obtain slurry A. S1.2 Pour slurry A into a mold with a heat-conducting plate at the bottom and let it stand; S1.3 Place the mold containing slurry A on an ultra-low temperature medium for cryogenic casting to quickly obtain solidified cement slurry B; S1.4 Thaw the solidified cement paste B to obtain block C, and then place block C in a cement curing box for 24-30 days to obtain cement-based material D with a directional pore structure.

7. The application of a low interfacial impedance cement-based zinc battery as described in any one of claims 1-6 in the field of building materials.

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