Electrolyte having cement-based structure and preparation method therefor

Abstract

The present invention provides an electrolyte having a cement-based structure and a preparation method therefor. Raw materials for the electrolyte having the cement-based structure include an inorganic gel material, a polymer monomer, polyacrylic acid, an initiator, and modified aluminosilicate zeolite, wherein the modified aluminosilicate zeolite is prepared by soaking aluminosilicate zeolite in a solution of a silicone-modified polyacrylate containing OH functional groups, taking out the aluminosilicate zeolite, performing heat treatment, and then soaking the aluminosilicate zeolite in a lithium salt solution, wherein the polymer monomer is a mixture of acrylamide and a long-carbon-chain alkyl acrylate hydrophobic monomer. In the present invention, by means of a synergistic hydrophobic effect of the modified aluminosilicate zeolite and a multi-component-copolymerized modified polyacrylamide, the dispersion of the polymer network in a cement paste is promoted, facilitating the formation of a uniformly distributed polymer network and the improvement of the ionic conductivity of the electrolyte; in addition, the modified aluminosilicate zeolite adsorbs a certain amount of a lithium salt, thereby contributing to the improvement of a discharge window of the electrolyte having the cement-based structure.

Description

A cement-based structural electrolyte and preparation method thereof Technical Field

[0001] The present invention relates to the technical field of cement-based structural energy storage integrated materials, and in particular to a cement-based structural electrolyte and a preparation method thereof. Background Art

[0002] Cement-based materials, as one of the most widely used man-made materials, are used in housing construction, roads, bridges, airports, and other fields due to their advantages, such as a wide range of raw material sources, excellent mechanical properties, and adaptability to a wide range of environments. With rapid economic development, people's demand for functional cement-based building materials is also increasing. Imparting good electrical conductivity to cement-based materials holds great potential for broad application. Cement-based structural energy storage materials for energy harvesting and health monitoring combine the excellent mechanical properties of cement-based materials with the ability to store electrical energy and conduct electrical signals. Conventional supercapacitors require separate energy storage units from the energy storage system. In some environments where space is limited, separate energy storage units waste space, leading to increased overall weight and cost. By combining structural and energy storage functions, a cement-based electrolyte that can both bear weight and conduct ions is being developed. This is crucial for better energy harvesting and utilization, as well as improving the self-sensing capabilities of structures.

[0003] Cement-based materials are inherently insulators, and the ionic conductivity of cement-based electrolytes can generally be improved by creating a suitable pore structure or adding a conductive medium. Existing research generally achieves this goal by adding polymers to cement materials, but the aggregation of polymers in cement systems has always limited the improvement of the ionic conductivity of cement-based electrolytes.

[0004] Chinese patent CN113436908A provides an idea for an in-situ polymer-generated cement-based electrolyte. Although its in-situ polymerization method breaks through the upper limit of polymer incorporation, since the triggering of its polymerization reaction requires cement hydration to provide heat, for some large-volume cement structures, the hydration heat release is uneven, resulting in an uneven polymer network, which greatly limits the improvement of ionic conductivity.

[0005] In summary, existing polymer-based cement-based structural electrolytes still have many problems, such as uneven polymer network distribution, narrow discharge window, low energy density, and poor feasibility for practical application.

[0006] Summary of the Invention

[0007] Purpose of the invention: In order to solve the problems of uneven polymer network distribution and narrow discharge window in existing cement-based structural electrolytes, the present application provides a cement-based structural electrolyte based on modified aluminum silicate zeolite. The cement-based structural electrolyte not only has higher ionic conductivity, but also has a wider discharge window, faster charge and discharge speed, and more cycle times.

[0008] Technical solution: In order to solve the above technical problems, the present invention adopts the following technical solution:

[0009] A cement-based structural electrolyte, wherein the raw materials of the cement-based structural electrolyte include an inorganic gel material, the inorganic gel material contains cement, and the raw materials of the cement-based structural electrolyte further include a polymer monomer, polyacrylic acid, an initiator, and modified aluminum silicate zeolite, wherein the mass ratio of the modified aluminum silicate zeolite to the inorganic gel material is 1:8-10;

[0010] The modified aluminosilicate is prepared by soaking aluminosilicate in a solution of organosilicon-modified polyacrylate containing OH functional groups, taking it out, heat-treating it, and then soaking it in a lithium salt solution;

[0011] The polymer monomer is a mixture of acrylamide and a long carbon chain alkyl acrylate hydrophobic monomer, and the mass ratio of acrylamide to the long carbon chain alkyl acrylate hydrophobic monomer is 1:0.5-1.5;

[0012] The polymer monomer dosage is 1% to 20% of the mass of the solid particles;

[0013] The polyacrylic acid is added in an amount of 2 to 7% of the mass of the solid particles;

[0014] The mass of the solid particles is the sum of the masses of the modified aluminosilicate zeolite and the inorganic gelling material.

[0015] In the present invention, the polymer monomer is in situ polymerized in the presence of an initiator and cement hydration exotherm during the cement hydration process to obtain a multi-component copolymerized modified polyacrylamide. The modified polyacrylamide is obtained by copolymerizing a hydrophobic monomer of a long carbon chain alkyl acrylate with a hydrophobic effect and acrylamide, and the modified polyacrylamide has a certain hydrophobic effect. In the cement paste, the hydrophobic groups in the modified polyacrylamide tend to associate into polymers, forming multiple hydrophobic microdomains, and as the amount of polymers increases, a spatial network structure is eventually formed. Compared to the in situ polymerization of acrylamide used in existing patents, the mixed monomers of monomers with hydrophobic groups, under the influence of hydrophobic action, form a polymer network in the cement paste that tends to be uniformly distributed.

[0016] In the present invention, the modified aluminosilicate is prepared by immersing the aluminosilicate in a solution of an organosilicon-modified polyacrylate containing OH functional groups. This coats the aluminosilicate surface with a layer of the organosilicon-modified polyacrylate, transforming the aluminosilicate's inherent hydrophilicity into a hydrophobic one. This hydrophobic modified aluminosilicate facilitates uniform distribution within the inorganic gelling material.

[0017] In the present invention, the synergistic hydrophobic effect of modified aluminosilicate zeolite and modified polyacrylamide can make the two phases uniformly dispersed in the cement paste, creating multiple channels for ion transmission, which is beneficial to improving the ionic conductivity of the cement-based structural electrolyte.

[0018] In some specific embodiments, the weight average molecular weight of the polyacrylic acid is 8,000 to 150,000.

[0019] According to some implementation aspects of the present invention, the raw materials of the cement-based structural electrolyte further include an inorganic salt, which accounts for 3-10% of the mass of the solid particles. Furthermore, the inorganic salt is lithium chloride.

[0020] According to some embodiments of the present invention, the lithium salt is an organic lithium salt.

[0021] In some specific embodiments, the lithium salt is one or a combination of Li[(CF3SO2)2N, Li[(FSO2)2N, Li[(FSO2)(n-C4F9SO2)N.

[0022] In some specific embodiments, the heat treatment temperature is 80-160° C., and the time is 2-24 hours.

[0023] In some specific embodiments, the mass ratio of the lithium salt solution to aluminosilicate is 1 to 3:1, and the concentration of the lithium salt solution is 15 to 25M.

[0024] In some specific embodiments, the solvent used in the solution of the organosilicon-modified polyacrylate containing OH functional groups is acetone. For example, the organosilicon-modified polyacrylate containing OH functional groups is BYK-SILCLEAN 3700.

[0025] In some specific embodiments, the solvent used in the lithium salt solution is acetonitrile.

[0026] In some specific embodiments, the concentration of the organosilicon-modified polyacrylate solution containing OH functional groups is 0.05 to 1 g / L.

[0027] In some specific embodiments, the modified aluminosilicate zeolite is prepared by soaking the aluminosilicate zeolite in the organosilicon-modified polyacrylate solution containing OH functional groups, washing the aluminosilicate zeolite, drying the aluminosilicate zeolite, heat-treating the aluminosilicate zeolite, soaking the aluminosilicate zeolite in a lithium salt solution, stirring the aluminosilicate zeolite, and filtering the aluminosilicate zeolite.

[0028] In some specific embodiments, the washing is performed using ethanol and water in sequence; and the stirring time is 10 to 14 hours.

[0029] In some embodiments, the polymer monomer content is 4-20% of the mass of the solid particles. Preferably, the polymer monomer content is 4-12% of the mass of the solid particles.

[0030] In some embodiments, the polymer monomer content is 10-20% of the mass of the solid particles; preferably, the polymer monomer content is 12-20% of the mass of the solid particles; further preferably, the polymer monomer content is 20% of the mass of the solid particles.

[0031] In some embodiments, the number of carbon atoms in the long carbon chain alkyl group is C8 to C 16. Preferably, the long carbon chain alkyl acrylate hydrophobic monomer is lauryl acrylate.

[0032] In some specific embodiments, the raw materials of the cement-based structural electrolyte further include a crosslinking agent, which is one or a combination of N,N'-methylenebisacrylamide and octadecyldimethylallyl ammonium chloride, and the amount of the crosslinking agent accounts for 0.0001 to 0.001% of the amount of the polymer monomer.

[0033] In some specific embodiments, the mass of the initiator accounts for 0.01 to 0.02% of the amount of the polymer monomer.

[0034] In some specific embodiments, the initiator is independently selected from one or a combination of ammonium persulfate, potassium persulfate, and sodium persulfate.

[0035] In some embodiments, the inorganic gel material further comprises an admixture, wherein the admixture is one or a combination of fly ash, mineral powder, and silica fume, wherein the cement accounts for 75-85% of the total weight of the inorganic gel material.

[0036] Preferably, the admixture is fly ash.

[0037] In some embodiments, the cement is 42.5 Portland cement.

[0038] In some embodiments, the raw materials of the cement-based structural electrolyte further include water, and the water accounts for 30% to 60% of the mass of the solid particles.

[0039] The discharge window improvement mechanism of the present invention is as follows: a high concentration of lithium salt as an electrolyte can reduce the proportion of free water, form a "salt-in-water" structure, inhibit the decomposition of water, and thus widen the voltage window.

[0040] The second technical solution adopted by the present invention is: the preparation method of the above-mentioned cement-based structural electrolyte comprises the following steps:

[0041] (1) mixing a polymer monomer, polyacrylic acid, an inorganic salt, an initiator, a cross-linking agent, and water to obtain a mixed solution;

[0042] (2) mixing the modified aluminosilicate zeolite and the inorganic gel material to obtain a powder;

[0043] (3) The mixed liquid and powder are mixed to obtain a slurry, and then the slurry is poured and cured.

[0044] In step (3), the curing includes steam curing and standard curing, the steam curing temperature is 50-70° C., and the time is 20-28 hours.

[0045] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0046] The present invention promotes the dispersion of the in-situ polymerized copolymer network in the cement paste through the synergistic hydrophobic effect of modified aluminum silicate zeolite and multi-component copolymerized modified polyacrylamide, helps to form a uniformly distributed polymer network, and promotes the improvement of the electrolyte ion conductivity. At the same time, the modified aluminum silicate zeolite adsorbs a certain amount of lithium salt, which to a certain extent increases the content of mobile ions in the cement-based structured electrolyte, inhibits the decomposition of water in the cement-based structured electrolyte, and improves the discharge window of the cement-based structured electrolyte.

[0047] The above summary is for illustrative purposes only and is not intended to be limiting in any way. In addition to the illustrative aspects, embodiments and features described above, further aspects, embodiments and features of the present application will be readily apparent by reference to the following detailed description. DETAILED DESCRIPTION

[0048] As described in the background technology, the existing polymer-based cement-based structural electrolyte has problems such as uneven distribution of polymer network and narrow discharge window. The present invention solves the above problems well by synergistically modifying aluminum silicate and modified polyacrylamide. First, the modified aluminum silicate itself has good hydrophobicity and can be evenly dispersed in cement paste; the modified polyacrylamide obtained by copolymerizing a hydrophobic monomer of a long carbon chain alkyl acrylate with a hydrophobic effect and acrylamide also has a certain hydrophobic effect. Compared with ordinary acrylamide in situ polymerization, it is susceptible to uneven hydration heat release and prone to agglomeration. The method of copolymerizing the composite hydrophobic monomer of the present invention is used, and the agglomeration phenomenon will be greatly reduced under the improvement of the hydrophobic effect. In addition, the organosilicon-modified polyacrylate carried on the modified aluminum silicate can play the role of traction polymer, so that the polymer network is more evenly dispersed in the cement paste, promoting the formation of the polymer network formed in the cement material to form a more even distribution, effectively reducing the impedance of the cement-based structural electrolyte, and greatly improving the ionic conductivity of the electrolyte system. At the same time, a certain amount of lithium salt can be pre-loaded on the modified aluminum silicate zeolite to increase the total amount of freely mobile ions in the cement-based electrolyte, and inhibit the decomposition of water through the salt-in-water structure, significantly improving the discharge window of the cement-based structural electrolyte.

[0049] The technical solutions of the present invention are described in detail below in conjunction with specific embodiments so that those skilled in the art can better understand and implement the technical solutions of the present invention, but the present invention is not limited to the scope of the examples.

[0050] The experimental methods in the following examples are conventional methods unless otherwise specified. The raw materials used in the following examples are commercially available products unless otherwise specified.

[0051] Example 1

[0052] This embodiment provides a cement-based structural electrolyte, which is prepared by the following method:

[0053] (1) 10 g of untreated aluminosilicate zeolite was immersed in a modified solution formed by blending 0.2 g / L of organosilicon-modified polyacrylate containing OH functional groups (specifically BYK-SILCLEAN 3700) and acetone, taken out and washed with ethanol, and placed in a vacuum oven at 120°C for 3 h;

[0054] Lithium salt Li[(CF3SO2)2N] was dissolved in acetonitrile to obtain 80 g of solution (the lithium salt concentration of the solution was 21 M), and then the treated aluminum silicate was immersed in the lithium salt solution, magnetically stirred for 12 hours, and then filtered. Then, it was repeatedly rinsed with ethanol and then rinsed with deionized water, and placed in an oven to dry at 50°C to obtain modified aluminum silicate.

[0055] (2) 5 g of polyacrylic acid (weight average molecular weight 100,000), 5 g of lithium chloride, 10 g of acrylamide, 10 g of lauryl acrylate, 0.0026 g of ammonium persulfate, and 0.000134 g of N,N'-methylenebisacrylamide were weighed and poured into 50 g of water and stirred to obtain a uniform mixed solution A.

[0056] (3) Weigh 90 g of inorganic cementitious material (specifically, a mixture of 72 g of 42.5 silicate cement and 18 g of fly ash) and 10 g of modified aluminosilicate zeolite, respectively, and pour them into a cement mortar mixer and stir at 250 rpm for 90 s to ensure that the powders are fully mixed to obtain powder B;

[0057] (4) Add the mixed solution into the stirring pot and stir it with powder B at 250 rpm for 90 s. After the stirring stops, scrape the mud from the blades and the pot wall into the middle of the pot, then switch to high-speed stirring mode and stir at 500 rpm for 60 s to obtain mixture C;

[0058] (5) The obtained mixture C was taken out and placed into a 20 mm × 20 mm × 20 mm mold. Then, the conductive graphite sheets were cut into 20 mm × 20 mm sizes and inserted into both ends of the block. The block was then placed in a steam curing box and cured at 60 ° C for 24 h.

[0059] (6) The mold containing the cured block was removed, and the portion that expanded above the mold surface was removed. After demolding, a cement-based structural electrolyte based on modified polymer and modified aluminum silicate zeolite with graphite sheet electrodes was obtained. The prepared cement-based structural electrolyte was placed in a standard cement curing room and cured for 28 days for testing of compressive strength and electrical properties.

[0060] Example 2

[0061] This embodiment provides a cement-based structural electrolyte, which is prepared by the following method:

[0062] (1) 5 g of untreated aluminosilicate was immersed in a modified solution formed by mixing 0.2 g / L BYK-SILCLEAN 3700 and acetone, taken out and washed with ethanol, and placed in a vacuum oven at 120°C for 3 h;

[0063] Lithium salt Li[(CF3SO2)2N] was dissolved in acetonitrile to obtain 80 g of solution (the lithium salt concentration of the solution was 21 M), and then the treated aluminum silicate was immersed in the lithium salt solution, magnetically stirred for 12 hours, and then filtered. Then, it was repeatedly rinsed with ethanol and then rinsed with deionized water, and placed in an oven to dry at 50°C to obtain modified aluminum silicate.

[0064] (2) Weigh 5 g of polyacrylic acid, 5 g of lithium chloride, 10 g of acrylamide, 10 g of lauryl acrylate, 0.0026 g of ammonium persulfate, and 0.000134 g of N,N'-methylenebisacrylamide, add them to 40 g of water, and stir evenly to prepare a uniform mixed solution A.

[0065] (3) Weigh 95 g of inorganic cementitious material (specifically, a mixture of 76 g of 42.5 silicate cement and 19 g of fly ash) and 10 g of modified aluminosilicate zeolite, respectively, and pour them into a cement mortar mixer and stir at 250 rpm for 90 s to ensure that the powders are fully mixed to obtain powder B;

[0066] (4) Add the mixed solution into the stirring pot and stir it with powder B at 250 rpm for 90 s. After the stirring stops, scrape the mud from the blades and the pot wall into the middle of the pot, then switch to high-speed stirring mode and stir at 500 rpm for 60 s to obtain mixture C;

[0067] (5) The obtained mixture C was taken out and placed into a 20 mm × 20 mm × 20 mm mold. Then, the conductive graphite sheets were cut into 20 mm × 20 mm sizes and inserted into both ends of the block. The block was then placed in a steam curing box and cured at 60 ° C for 24 h.

[0068] (6) The mold containing the cured block was removed, and the portion that expanded above the mold surface was removed. After demolding, a cement-based structural electrolyte based on modified polymer and modified aluminum silicate zeolite with graphite sheet electrodes was obtained. The prepared cement-based structural electrolyte was placed in a standard cement curing room and cured for 28 days for testing of compressive strength and electrical properties.

[0069] Example 3

[0070] This embodiment provides a cement-based structural electrolyte, which is prepared by the following method:

[0071] (1) 10 g of untreated aluminosilicate was immersed in a modified solution formed by mixing 0.2 g / L BYK-SILCLEAN 3700 and acetone, taken out and washed with ethanol, and placed in a vacuum oven at 120°C for 3 h;

[0072] Lithium salt Li[(CF3SO2)2N] was dissolved in acetonitrile to obtain 80 g of solution (the lithium salt concentration of the solution was 21 M), and then the treated aluminum silicate was immersed in the lithium salt solution, magnetically stirred for 12 hours, and then filtered. Then, it was repeatedly rinsed with ethanol and then rinsed with deionized water, and placed in an oven to dry at 50°C to obtain modified aluminum silicate.

[0073] (2) Weigh 5 g of polyacrylic acid, 5 g of lithium chloride, 5 g of acrylamide, 5 g of lauryl acrylate, 0.0013 g of ammonium persulfate, and 0.000067 g of N,N'-methylenebisacrylamide, add them to 50 g of water, and stir evenly to prepare a uniform mixed solution A.

[0074] (3) Weigh 90 g of inorganic cementitious material (specifically, a mixture of 72 g of 42.5 silicate cement and 18 g of fly ash) and 10 g of modified aluminosilicate zeolite, respectively, and pour them into a cement mortar mixer and stir at 250 rpm for 90 s to ensure that the powders are fully mixed to obtain powder B;

[0075] (4) Add the mixed solution into the stirring pot and stir it with powder B at 250 rpm for 90 s. After the stirring stops, scrape the mud from the blades and the pot wall into the middle of the pot, then switch to high-speed stirring mode and stir at 500 rpm for 60 s to obtain mixture C;

[0076] (5) The obtained mixture C was taken out and placed into a 20 mm × 20 mm × 20 mm mold. Then, the conductive graphite sheets were cut into 20 mm × 20 mm sizes and inserted into both ends of the block. The block was then placed in a steam curing box and cured at 60 ° C for 24 h.

[0077] (6) The mold containing the cured block was removed, and the portion that expanded above the mold surface was removed. After demolding, a cement-based structural electrolyte based on modified polymer and modified aluminum silicate zeolite with graphite sheet electrodes was obtained. The prepared cement-based structural electrolyte was placed in a standard cement curing room and cured for 28 days for testing of compressive strength and electrical properties.

[0078] Example 4

[0079] This embodiment provides a cement-based structural electrolyte, which is prepared by the following method:

[0080] (1) 10 g of untreated aluminosilicate was immersed in a modified solution formed by mixing 0.2 g / L BYK-SILCLEAN 3700 and acetone, taken out and washed with ethanol, and placed in a vacuum oven at 120°C for 3 h;

[0081] Lithium salt Li[(CF3SO2)2N] was dissolved in acetonitrile to obtain 80 g of solution (the lithium salt concentration of the solution was 21 M), and then the treated aluminum silicate was immersed in the lithium salt solution, magnetically stirred for 12 hours, and then filtered. Then, it was repeatedly rinsed with ethanol and then rinsed with deionized water, and placed in an oven to dry at 50°C to obtain modified aluminum silicate.

[0082] (2) Weigh 5 g of polyacrylic acid, 5 g of lithium chloride, 2.5 g of acrylamide, 2.5 g of lauryl acrylate, 0.00065 g of ammonium persulfate, and 0.0000335 g of N,N'-methylenebisacrylamide, add them to 50 g of water, and stir evenly to prepare a uniform mixed solution A.

[0083] (3) Weigh 90 g of inorganic cementitious material (specifically, a mixture of 72 g of 42.5 silicate cement and 18 g of fly ash) and 10 g of modified aluminosilicate zeolite, respectively, and pour them into a cement mortar mixer and stir at 250 rpm for 90 s to ensure that the powders are fully mixed to obtain powder B;

[0084] (4) Add the mixed solution into the stirring pot and stir it with powder B at 250 rpm for 90 s. After the stirring stops, scrape the mud from the blades and the pot wall into the middle of the pot, then switch to high-speed stirring mode and stir at 500 rpm for 60 s to obtain mixture C;

[0085] (5) The obtained mixture C was taken out and placed into a 20 mm × 20 mm × 20 mm mold. Then, the conductive graphite sheets were cut into 20 mm × 20 mm sizes and inserted into both ends of the block. The block was then placed in a steam curing box and cured at 60 ° C for 24 h.

[0086] (6) The mold containing the cured block was removed, and the portion that expanded above the mold surface was removed. After demolding, a cement-based structural electrolyte based on modified polymer and modified aluminum silicate zeolite with graphite sheet electrodes was obtained. The prepared cement-based structural electrolyte was placed in a standard cement curing room and cured for 28 days for testing of compressive strength and electrical properties.

[0087] Example 5

[0088] The cement-based structural electrolyte provided in this embodiment is basically the same as that in Example 1, except that: in step (1), the lithium salt dissolved in acetonitrile is replaced with a mixture of Li[(FSO2)2N and Li[(FSO2)(n-C4F9SO2)N, and the concentration remains unchanged.

[0089] Example 6

[0090] The cement-based structural electrolyte provided in this embodiment is different from that in embodiment 1 in that octadecyldimethylallyl ammonium chloride is used in step (2) instead of N,N'-methylenebisacrylamide.

[0091] Example 7

[0092] This embodiment provides a cement-based structural electrolyte, which is basically the same as that of Example 1, except that the 18g fly ash added in step (3) is replaced with 9g mineral powder and 9g silica fume.

[0093] Comparative Example 1

[0094] The cement-based structural electrolyte provided in this comparative example is substantially the same as that in Example 1, except that the polyacrylate modification procedure of the aluminosilicate zeolite in step (1) is omitted;

[0095] In step (3), 90 g of inorganic gelling material (specifically, a mixture of 72 g of 42.5 silicate cement and 18 g of fly ash) and 10 g of aluminosilicate zeolite were weighed, poured into a cement mortar mixer and stirred at 250 rpm for 90 s to ensure that the powders were fully mixed to obtain powder B.

[0096] Comparative Example 2

[0097] The cement-based structured electrolyte provided in this comparative example is substantially the same as that in Example 1, except that: step (1) is omitted, and the amount of aluminosilicate zeolite is reduced to 0;

[0098] In step (2), the solute water was changed from 50 g to 40 g;

[0099] In step (3), the amount of inorganic gelling material is increased from 90 g to 100 g (specifically, a mixture of 80 g of 42.5 silicate cement and 20 g of fly ash).

[0100] Comparative Example 3

[0101] The cement-based structural electrolyte provided in this comparative example is substantially the same as that of Example 4, except that the addition of the mixed polymer monomers and the corresponding initiator and cross-linking agent in step (2) is omitted.

[0102] The cement-based structured electrolytes based on modified polymers and modified aluminosilicate, equipped with graphite sheet electrodes, prepared in the above examples were subjected to compressive strength and electrical performance tests. The compressive strength test of the cement-based structured electrolyte was conducted on a universal concrete testing machine, while the electrical performance test was primarily conducted using an electrochemical workstation using AC impedance spectroscopy. Specific performance data are shown in Table 1.

[0103] Table 1 Performance data of electrolytes of Examples 1 to 7 and Comparative Examples 1 to 3

[0104] The above embodiments are intended only to illustrate the technical concepts and features of the present invention. Their purpose is to enable those skilled in the art to understand the contents of the present invention and implement them accordingly. They are not intended to limit the scope of protection of the present invention. Any equivalent changes or modifications made in accordance with the spirit of the present invention are intended to be covered by the scope of protection of the present invention.

[0105] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

Claims

1. A cement-based structural electrolyte, wherein the raw materials of the cement-based structural electrolyte include an inorganic gel material, and the inorganic gel material contains cement, characterized in that: The raw materials of the cement-based structural electrolyte also include polymer monomers, polyacrylic acid, initiators and modified aluminum silicate zeolite, and the mass ratio of the modified aluminum silicate zeolite to the inorganic gel material is 1:8-10; The modified aluminum silicate zeolite is prepared by soaking the aluminum silicate zeolite in a solution of an organosilicon-modified polyacrylate containing an OH functional group, taking it out, heat-treating it, and then soaking it in a lithium salt solution; The lithium salt is one or a combination of Li[(CF3SO2)2N, Li[(FSO2)2N, Li[(FSO2)(n-C4F9SO2)N; The polymer monomer is a mixture of acrylamide and a long-chain alkyl acrylate hydrophobic monomer, and the mass ratio of the acrylamide to the long-chain alkyl acrylate hydrophobic monomer is 1:0.5-1.5; The polymer monomer dosage is 12-20% of the mass of the solid particles; The polyacrylic acid is added in an amount of 2 to 7% of the mass of the solid particles; The mass of the solid particles is the sum of the masses of the modified aluminosilicate zeolite and the inorganic gelling material; The inorganic gel material further comprises an admixture, wherein the admixture is fly ash, wherein the cement accounts for 75-85% of the total weight of the inorganic gel material; The number of carbon atoms in the long carbon chain alkyl is C8 to C16; The raw materials of the cement-based structural electrolyte also include a crosslinking agent, and the amount of the crosslinking agent accounts for 0.0001-0.001% of the amount of the polymer monomer.

2. The cement-based structural electrolyte according to claim 1, characterized in that: The polymer monomer content is 20% of the mass of the solid particles.

3. A cement-based structural electrolyte, wherein the raw materials of the cement-based structural electrolyte include an inorganic gel material, and the inorganic gel material contains cement, characterized in that: The raw materials of the cement-based structural electrolyte also include polymer monomers, polyacrylic acid, initiators and modified aluminum silicate zeolite, and the mass ratio of the modified aluminum silicate zeolite to the inorganic gel material is 1:8-10; The modified aluminum silicate zeolite is prepared by soaking the aluminum silicate zeolite in a solution of an organosilicon-modified polyacrylate containing an OH functional group, taking it out, heat-treating it, and then soaking it in a lithium salt solution; The polymer monomer is a mixture of acrylamide and a long-chain alkyl acrylate hydrophobic monomer, and the mass ratio of the acrylamide to the long-chain alkyl acrylate hydrophobic monomer is 1:0.5-1.5; The polymer monomer dosage is 1% to 20% of the mass of the solid particles; The polyacrylic acid is added in an amount of 2 to 7% of the mass of the solid particles; The mass of the solid particles is the sum of the masses of the modified alumina silicalite and the inorganic gelling material.

4. The cement-based structural electrolyte according to claim 3, characterized in that: The polymer monomer content is 4-20% of the mass of the solid particles.

5. The cement-based structural electrolyte according to claim 4, characterized in that: The polymer monomer dosage is 4-12% of the mass of the solid particles.

6. The cement-based structural electrolyte according to claim 3, characterized in that: The polymer monomer content is 10-20% of the mass of the solid particles; preferably, the polymer monomer content is 12-20% of the mass of the solid particles; further preferably, the polymer monomer content is 20% of the mass of the solid particles.

7. The cement-based structural electrolyte according to claim 3, characterized in that: The number of carbon atoms in the long carbon chain alkyl is C8 to C16.

8. The cement-based structural electrolyte according to claim 7, characterized in that: The long carbon chain alkyl acrylate hydrophobic monomer is lauryl acrylate.

9. The cement-based structural electrolyte according to claim 3, characterized in that: The raw materials of the cement-based structural electrolyte also include a crosslinking agent, and the amount of the crosslinking agent accounts for 0.0001-0.001% of the amount of the polymer monomer.

10. The cement-based structural electrolyte according to claim 9, characterized in that: The cross-linking agent is one of N,N'-methylenebisacrylamide and octadecyldimethylallyl ammonium chloride or a combination of the two.

11. The cement-based structural electrolyte according to claim 3, characterized in that: The mass of the initiator accounts for 0.01-0.02% of the mass of the polymer monomer.

12. The cement-based structural electrolyte according to claim 3, characterized in that: The initiators are independently selected from one or a combination of ammonium persulfate, potassium persulfate, and sodium persulfate.

13. The cement-based structural electrolyte according to claim 3, characterized in that: The raw materials of the cement-based structural electrolyte also include inorganic salts, and the inorganic salts account for 3-10% of the mass of the solid particles.

14. The cement-based structural electrolyte according to claim 13, characterized in that: The inorganic salt is lithium chloride.

15. The cement-based structural electrolyte according to claim 3, characterized in that: The lithium salt is an organic lithium salt.

16. The cement-based structural electrolyte according to claim 15, characterized in that: The lithium salt is one or a combination of Li[(CF3SO2)2N, Li[(FSO2)2N, Li[(FSO2)(n-C4F9SO2)N.

17. The cement-based structural electrolyte according to claim 3, characterized in that: The weight average molecular weight of the polyacrylic acid is 8,000 to 150,000.

18. The cement-based structural electrolyte according to claim 3, characterized in that: The heat treatment temperature is 80 to 160° C. and the time is 2 to 24 hours; and / or, The concentration of the lithium salt solution is controlled to be 15-25M; The solvent used in the organic silicon modified polyacrylate solution containing OH functional groups is acetone; The solvent used in the lithium salt solution is acetonitrile.

19. The cement-based structural electrolyte according to any one of claims 15 to 18, characterized in that: The modified aluminum silicate zeolite is prepared by soaking the aluminum silicate zeolite in the organosilicon-modified polyacrylate solution containing OH functional groups, taking it out, washing it, drying it, and then heat-treating it, and then soaking it in the lithium salt solution and stirring it, and filtering it, wherein the washing is carried out in sequence with ethanol and water respectively; and the stirring time is 10 to 14 hours.

20. The cement-based structural electrolyte according to claim 3, characterized in that: The inorganic gel material further comprises an admixture, which is one or a combination of fly ash, mineral powder and silica ash, wherein the cement accounts for 75-85% of the total weight of the inorganic gel material.

21. The cement-based structural electrolyte according to claim 20, characterized in that: The admixture is fly ash.

22. The cement-based structural electrolyte according to claim 3, characterized in that: The raw materials of the cement-based structural electrolyte also include water, and the water accounts for 30% to 60% of the mass of the solid particles.

23. The cement-based structural electrolyte according to claim 3, characterized in that: The raw materials of the cement-based structural electrolyte also include inorganic salt, water and a cross-linking agent. The preparation method of the cement-based structural electrolyte includes the following steps: (1) mixing a polymer monomer, polyacrylic acid, an inorganic salt, an initiator, a cross-linking agent and water to obtain a mixed solution; (2) mixing the modified aluminosilicate zeolite and the inorganic gel material to obtain a powder; (3) The mixed liquid and the powder are mixed to obtain a slurry, and then the slurry is poured and cured.

24. A method for preparing the cement-based structural electrolyte according to any one of claims 3 to 12 and 15 to 21, characterized in that: The raw materials of the cement-based structural electrolyte also include inorganic salts and water, and the method comprises the following steps: (1) mixing a polymer monomer, polyacrylic acid, an inorganic salt, an initiator, a cross-linking agent and water to obtain a mixed solution; (2) mixing the modified aluminosilicate zeolite and the inorganic gel material to obtain a powder; (3) The mixed liquid and the powder are mixed to obtain a slurry, and then the slurry is poured and cured.

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