Solid waste-based structural electrolyte and structural supercapacitive energy storage battery comprising the same

Abstract

The application discloses a solid waste-based structural electrolyte and a structural supercapacitor energy storage battery containing the same, and belongs to the technical field of solid waste resource utilization and structural energy storage devices. The electrolyte comprises a gelled solid, a powder activator and a liquid-retaining material preloaded with an electrolyte, and a structural supercapacitor energy storage battery in a laminated configuration is prepared by using the electrolyte. Compared with the existing cement-based / concrete-based structural energy storage scheme, the application adopts a full-solid-waste gelled system composed of desulfurization gypsum, slag and steel slag to replace cement clinker, and takes into account the resource utilization and low-carbon attributes; the liquid content and ion strength of the electrolyte are dynamically buffered by the liquid-retaining material, the ion channel degradation and interface impedance rise caused by drying are slowed down, and therefore the capacitance retention rate and operation stability in a dry or dry-wet fluctuating environment are improved; the powder activator and the laminated configuration are more suitable for pre-mixed material and component construction, and are suitable for engineering amplification and quality consistency control.

Description

Technical Field

[0001] This invention relates to the field of solid waste resource utilization and structural energy storage device technology, specifically to a solid waste-based structural electrolyte and a structural supercapacitor energy storage battery containing the same. Background Technology

[0002] With the development of distributed energy, building-integrated energy storage, and intelligent infrastructure, "structural energy storage" technology, which combines energy storage functions with building materials or structural components, is gradually gaining attention. Compared to traditional electrochemical battery cells, the value of structural energy storage devices lies not only in energy or power output, but also in their ability to be integrated with the load-bearing structure, thereby achieving space saving, system simplification, and functional integration in scenarios such as wall panels, road surfaces, foundation components, and prefabricated components.

[0003] In existing research and engineering explorations, cement-based / concrete-based energy storage devices mainly utilize the porous network formed after the cementitious material is cured as an ion migration channel, allowing the pore solution or external electrolyte to form a quasi-solid electrolyte inside the material. Energy storage and release are achieved by configuring electrode layers and current collectors on both sides of the device. This type of scheme can usually form supercapacitors or low-cost electrochemical energy storage units. The device structure often adopts a stacked configuration of current collector / electrode layer / cemented electrolyte layer / electrode layer / current collector. The electrode layer is mostly a carbon-based material system (such as activated carbon, carbon black, graphite, graphene, carbon nanotubes, etc.), and the current collector can be metal mesh, foamed metal, or carbon cloth, etc.

[0004] However, existing cement-based / concrete-based energy storage devices still face a series of key bottlenecks when transitioning to engineering environments. First, the ion conduction of cementitious materials is highly sensitive to liquid content. When devices are in long-term dry or fluctuating wet / dry environments, moisture in the pores of the cementitious material gradually dissipates, causing effective ion channels to shrink or even cease. This leads to problems such as increased interfacial impedance, distortion of charge-discharge curves, and rapid capacity or capacitance decay. This problem is particularly pronounced in thin components, components with exposed edges, or high-temperature, low-humidity environments, and often manifests as an unstable phenomenon of "acceptable initial performance, but rapid performance degradation after drying," making it difficult to stably extrapolate the electrochemical performance under laboratory conditions to engineering service conditions.

[0005] Secondly, to improve the rate performance or reduce internal resistance of devices, some solutions tend to introduce conductive fillers (such as carbon black, carbon fiber, graphite, etc.) into the gelled electrolyte system to construct an electron conduction network. However, the introduction of the conductive phase also brings new contradictions: when the conductive network is continuously connected in the electrolyte bulk phase, it is easy to form an electron leakage path, thereby inducing self-discharge, short-circuit risk, or rapid decay of open-circuit voltage. In other words, the core role of gelled electrolytes in structural energy storage devices should be to provide a stable ion transport environment and play an isolation role; the conductive phase is more suitable to be arranged in the electrode layer or current collector layer to realize the construction of electron collection and reaction interface, rather than simply improving the electronic conductivity of the electrolyte bulk phase to reduce apparent resistance (otherwise it will directly increase the risk of self-discharge). That is, if it is necessary to enhance electron conduction, it should be achieved through carbon-based electrode layers (such as carbon black, etc.) or current collector design, rather than making the electrolyte material conductive as a whole.

[0006] Furthermore, from the perspective of low carbon and resource utilization, the traditional silicate cement clinker production process has a high carbon emission intensity, which limits the potential for the promotion of energy storage building materials under dual carbon targets. At the same time, the power, steel and other industrial systems generate large quantities of solid waste such as desulfurization gypsum, slag, and steel slag, and their utilization paths are mostly concentrated on low-value-added disposal. If these can be used as key material systems for structural energy storage devices (for example, as load-bearing electrolyte skeletons), it can not only reduce material costs and environmental burden, but also has the potential to achieve multi-scale structural integration at the component level.

[0007] In summary, existing technologies urgently need a solution that can achieve the following objectives: First, to construct a solid waste-based carrier gel electrolyte framework without relying on cement clinker, thereby achieving low carbon emissions and resource utilization; Second, to maintain the effective liquid content and ion transport continuity of the electrolyte under engineering environments (especially dry or wet-dry cycle conditions), thereby suppressing the growth of interfacial impedance and the degradation of electrochemical performance; Third, to avoid uncontrolled electronic connectivity pathways in the electrolyte bulk phase at the device structure design level, reducing the risk of self-discharge and short circuits, and to form a reliable stacked configuration with the carbon-based electrode layer and current collector. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention provides a solid waste-based structural electrolyte and a structural supercapacitor energy storage battery containing the same, aiming to achieve low-carbon solid waste resource utilization while also possessing high capacitance retention and low self-discharge risk under dry conditions.

[0009] In a first aspect, the present invention provides a solid waste-based structural electrolyte, comprising: a gelled solid, a powdered activator, and a liquid-retaining material; wherein, The cementitious solids, by weight, include: 5-35 parts of desulfurized gypsum, 30-80 parts of granulated blast furnace slag, and 10-60 parts of steel slag; The powder activator comprises: an alkaline compound and a sulfate, and the dosage of the powder activator is 2% to 15% of the mass of the gel solids; The liquid-retaining material is pre-loaded with electrolyte and has the ability to reversibly absorb and release electrolyte. The amount of the liquid-retaining material is 0.05% to 10% of the mass of the gel solid.

[0010] Furthermore, the cementitious solid also includes at least one of silica fume, fly ash, and metakaolin, and the total amount of silica fume, fly ash, and metakaolin is 0 to 20 parts by mass.

[0011] Furthermore, the amount of the powder activator is 4% to 8% of the mass of the gelled solid.

[0012] Furthermore, the alkaline compound is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; the sulfate is sodium sulfate and / or potassium sulfate.

[0013] Furthermore, the mass ratio of the alkaline compound to the sulfate is 9:1 to 1:9.

[0014] Furthermore, the powder activator is a powder composed of sodium hydroxide and sulfate, a powder composed of a premix of sodium hydroxide and inert filler and sulfate, or a powder composed of a premix of sodium hydroxide and soluble salt and sulfate.

[0015] Furthermore, the solid waste-based electrolyte is subjected to water extraction at a solid-liquid ratio of 1:5 to 1:20, and the pH of the resulting extract is in the range of 11.5 to 13.5.

[0016] Furthermore, the liquid-retaining material is selected from one or more of the following: Superabsorbent resin particles, with an admixture amount of 0.05% to 2.0% of the mass of the gelled solids; Hydrogel microspheres or microcapsules, at a dosage of 0.1% to 5.0% of the mass of the gelled solids; Porous carrier particles, wherein the porous carrier particles are bentonite, zeolite and / or biochar, and the dosage is 0.5% to 10% of the mass of the cementitious solids.

[0017] Furthermore, the electrolyte pre-loaded in the liquid-retaining material is an aqueous solution of at least one salt selected from sodium sulfate, potassium sulfate, sodium chloride, and potassium chloride, or a mixed aqueous solution of several of these salts; wherein the concentration of the pre-loaded electrolyte is 0.5 M to 2 M.

[0018] Furthermore, the liquid-retaining material is immersed in the electrolyte until it becomes saturated with the liquid and the surface free liquid is removed.

[0019] Furthermore, the liquid-retaining material is distributed in a gradient along the thickness direction of the solid waste-based electrolyte, wherein the content of the liquid-retaining material is higher in the region near the electrode interface than in the region far from the electrode interface.

[0020] In a second aspect, the present invention provides a structural supercapacitor energy storage battery, wherein the structural supercapacitor energy storage battery is a stacked configuration, comprising: a first current collector, a first electrode layer, a structural electrolyte layer, a second electrode layer, and a second current collector; The structured electrolyte layer uses the aforementioned solid waste-based structured electrolyte.

[0021] Furthermore, the electrode layer is a carbon-based electrode layer, and its material is selected from one or more of activated carbon, carbon black, graphite, graphene, and carbon nanotubes.

[0022] Furthermore, the current collector is selected from titanium mesh, nickel foam, carbon cloth, conductive polymer film or stainless steel mesh.

[0023] Furthermore, an interface transition layer is provided between the electrode layer and the structural electrolyte layer, the interface transition layer being a high-porosity gelled thin layer and / or a thin layer containing the liquid-retaining material.

[0024] Furthermore, the periphery of the supercapacitor energy storage battery is provided with an alkali-resistant sealing edge structure to suppress water loss from the electrolyte layer of the structure.

[0025] A third aspect of the present invention provides a method for preparing the above-described supercapacitor energy storage battery, comprising: The desulfurized gypsum, the granulated blast furnace slag and the steel slag are dry-mixed according to the above-mentioned mass fractions to obtain the cementitious solid. The powder activator is added to the gelled solid and dry-mixed to obtain a mixture; wherein the total amount of the powder activator is 2% to 15% of the mass of the gelled solid; The liquid-retaining material is pre-loaded with electrolyte until it is saturated with liquid and the surface free liquid is removed before being added to the mixture. Water is then added and stirred to obtain a slurry. The slurry is molded and cured to obtain a structural electrolyte layer; An electrode layer is prepared and combined with a current collector, and the electrolyte layer is sandwiched between the two electrode layers to form a stacked structure. The stacked structure is pressed together and the periphery is sealed with an alkali-resistant seal to obtain the supercapacitor energy storage battery structure.

[0026] Furthermore, by enriching the liquid-retaining material in the region near the electrode interface, and / or by providing the high-porosity gel layer between the electrode layer and the structural electrolyte layer, the region near the electrode interface can have a higher liquid content and / or a lower interfacial impedance.

[0027] A fourth aspect of the present invention provides the application of the above-described structural supercapacitor energy storage battery in building components, prefabricated wall panels, or road components.

[0028] Compared with the prior art, the present invention has at least the following beneficial effects: The solid waste-based structural electrolyte provided by this invention uses a solid waste cementitious system composed of desulfurized gypsum, slag, and steel slag to replace cement clinker as the carrier electrolyte skeleton of the structural supercapacitor, taking into account both resource utilization and low carbon attributes. A liquid-retaining material dynamically buffers the electrolyte liquid content and ionic strength, mitigating ion channel degradation and interfacial impedance increases caused by drying, thereby improving capacitance retention and operational stability under dry or fluctuating wet / dry conditions. The use of powdered activators facilitates dry activation, making pre-mixing and modular construction easier, suitable for engineering scale-up and quality consistency control. The stacked configuration of the structural supercapacitor energy storage battery is easier to construct modularly, suitable for engineering scale-up and quality consistency control. The division of labor between the electrodes / current collectors (which handle electron channels) and the electrolyte layer (which handles ion channels) avoids the formation of uncontrolled electron leakage pathways in the electrolyte bulk phase, helping to reduce self-discharge risk and improve device safety margins. Attached Figure Description

[0029] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments recorded in the embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings.

[0030] Figure 1 This is a comparison chart of ionic conductivity changes provided for embodiments and comparative examples of the present invention; Figure 2 Comparison diagrams of surface capacitance changes provided for embodiments and comparative examples of the present invention; Figure 3 A comparison chart of capacitance retention rate changes is provided for embodiments and comparative examples of the present invention; Figure 4 The diagram shows a comparison of the compressive strength changes for the embodiments and comparative examples of the present invention. Detailed Implementation

[0031] To better understand the above technical solutions, the technical solutions of the embodiments of this application will be described in detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the embodiments of this application and the specific features in the embodiments are detailed descriptions of the technical solutions of the embodiments of this application, rather than limitations on the technical solutions of this application. In the absence of conflict, the embodiments of this application and the technical features in the embodiments can be combined with each other.

[0032] A first aspect of this invention provides a solid waste-based structural electrolyte, comprising: a gelled solid, a powdered activator, and a liquid-retaining material; wherein, The cementitious solids, by weight, include: 5-35 parts desulfurized gypsum, 30-80 parts granulated blast furnace slag, and 10-60 parts steel slag; The powder activator includes alkaline compounds and sulfates, and the dosage of the powder activator is 2% to 15% of the mass of the gelled solids. The liquid-retaining material is pre-loaded with electrolyte and has the ability to reversibly absorb and release electrolyte. The amount of liquid-retaining material is 0.05% to 10% of the mass of the gel solids.

[0033] The solid waste-based structural electrolyte provided in this invention uses a solid waste cementitious system composed of desulfurized gypsum, slag, and steel slag to replace cement clinker as the load-bearing electrolyte skeleton of the structural supercapacitor, taking into account both resource utilization and low-carbon properties. By using liquid-retaining materials to dynamically buffer the electrolyte liquid content and ionic strength, the degradation of ion channels and the increase in interfacial impedance caused by drying are mitigated, thereby improving the capacitance retention rate and operational stability under dry or fluctuating wet and dry environments. The use of powder activators makes dry activation easier for pre-mixed materials and modular construction, which is suitable for engineering scale-up and quality consistency control.

[0034] Optionally, to address the fluctuations in chemical composition of solid waste from different sources, the composition of major oxides can be obtained through XRF or equivalent methods, and the overall composition of the gelled solids can be controlled within a preferred range. Preferably, the gelled solids contain: CaO 30 wt%~55 wt%, SiO2 20 wt%~40 wt%, Al2O3 5 wt%~18 wt%, and SO3 2 wt%~15 wt%; or the proportions can be fine-tuned through key molar ratio constraints (such as Ca / Si, Al / Si, S / Ca) to ensure the stability of the system's reaction pathway and the ionic environment of the pore solution.

[0035] Preferably, the cementitious solids include, by weight, 10-30 parts of desulfurized gypsum, 40-70 parts of granulated blast furnace slag, and 15-40 parts of steel slag.

[0036] In some embodiments, the cementitious solids further include at least one of silica fume, fly ash, and metakaolin, and the total amount of silica fume, fly ash, and metakaolin is 0 to 20 parts by mass.

[0037] Specifically, the pore structure of the gel solid is controlled by adding silica fume, fly ash, and metakaolin.

[0038] Preferably, the amount of powder activator is 4% to 8% of the mass of the gelled solids.

[0039] In some embodiments, the alkaline compound is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; the sulfate is sodium sulfate and / or potassium sulfate.

[0040] Specifically, Na and K sources can be interchanged. For example, a mild excitation route can be used for the excitation system, such as a combination of Na2CO3 and Na2SO4. An enhanced excitation route can also be used for the excitation system, such as a combination of NaOH and Na2SO4. When NaOH and Na2SO4 are combined, the preferred mass ratio of basic compound to sulfate is (8~10):1.

[0041] To ensure repeatability and feasibility, the mass ratio of alkaline compound to sulfate can be controlled within the range of 9:1 to 1:9. Its effective alkalinity is constrained by the total amount of powder activator and the pH window of the electrolyte extract.

[0042] Optionally, the powder activator is a powder composed of sodium hydroxide and sulfate, a powder composed of a premix of sodium hydroxide and inert filler and sulfate, or a powder composed of a premix of sodium hydroxide and soluble salt and sulfate.

[0043] In some embodiments, the solid waste-based structural electrolyte is subjected to water leaching at a solid-liquid ratio of 1:5 to 1:20, and the pH of the resulting extract is in the range of 11.5 to 13.5.

[0044] Specifically, to ensure the stability and repeatability of the system reaction, the pH of the extract of the mixed electrolyte slurry is controlled within the range of 11.5 to 13.5 (for example, sampling and extraction determination is performed 24 hours after mixing), thereby avoiding excessive fluctuations in solution alkalinity due to differences in the type of alkali source or the compounding ratio.

[0045] In some embodiments, the liquid-retaining material is a reversible liquid-absorbing and liquid-releasing component pre-loaded with electrolyte, that is, the liquid-retaining material can spontaneously absorb electrolyte (liquid absorption) or release electrolyte (liquid release), selected from one or more of the following: Superabsorbent resin particles, with an admixture dosage of 0.05%~2.0% of the mass of the gelled solids; Hydrogel microspheres or microcapsules, with an admixture content of 0.1% to 5.0% of the mass of the gelled solids; Porous carrier particles, which are bentonite, zeolite and / or biochar, are added at a rate of 0.5% to 10% of the mass of the cementitious solids.

[0046] Optionally, the electrolyte preloaded in the liquid-retaining material is an aqueous solution of at least one salt selected from sodium sulfate, potassium sulfate, sodium chloride, and potassium chloride, or a mixed aqueous solution of several of these salts; wherein the concentration of the preloaded electrolyte is 0.5 M to 2 M.

[0047] Specifically, the key to pre-loading the electrolyte lies in the fact that the electrolyte-retaining material not only stores water but also stores electrolyte with a certain ionic strength, thus simultaneously mitigating the negative impacts of decreased liquid content and changes in ion concentration on electrochemical performance during the drying process. The electrolyte-retaining material can be uniformly dispersed within the electrolyte layer; or it can form a gradient distribution region along the thickness direction: a higher content of electrolyte-retaining material near the electrode side to reduce interfacial impedance and improve rate capability; and a lower content of electrolyte-retaining material in the central support region to ensure strength and reduce the risk of electron leakage. Understandably, the central support region has lower electronic conductivity, which can be achieved by: the central support region not containing a continuous conductive filler network; and / or the volume resistivity of the central support region being higher than that of the region near the electrode interface.

[0048] Superabsorbent polymer (SAP) particles are small particles capable of absorbing water, exhibiting strong liquid absorption, rapid liquid release response, and high liquid storage capacity. They are first soaked in electrolyte to saturate the particles before being added to the gelation system. Unless otherwise specified, the superabsorbent polymer particles used in this embodiment are cross-linked polyacrylates with a particle size of 100 μm to 600 μm and a water absorption rate of 1 to 5 g / g, exhibiting alkali resistance. Hydrogel microspheres are hydrophilic polymer microparticles with a cross-linked network. Hydrogel microspheres achieve liquid absorption and release through swelling / shrinkage; compared to SAP, this type of material can achieve a more "slow-release" liquid supply behavior or a more stable liquid storage form. Porous carrier particles are solid particles with a well-developed pore structure (micropores / mesopores / capillaries), used to store electrolyte through pore adsorption or capillary action. Porous carriers achieve "liquid absorption" through capillary adsorption and pore storage, releasing the liquid within the pores through capillary pressure difference when the external environment is dry or pore water decreases. Unless otherwise specified, the zeolite in the embodiments of the present invention is natural clinoptilolite or synthetic zeolite with a particle size of 50 μm to 500 μm and a water absorption rate greater than 0.15 g / g.

[0049] In some embodiments, the liquid-retaining material is immersed in the electrolyte until it becomes saturated with the liquid and the surface free liquid is removed.

[0050] A second aspect of the present invention provides a structural supercapacitor energy storage battery, which has a stacked configuration, including: a first current collector, a first electrode layer, a structural electrolyte layer, a second electrode layer, and a second current collector; wherein the structural electrolyte layer is made of the aforementioned solid waste-based structural electrolyte.

[0051] The structural supercapacitor energy storage battery provided by this invention adopts a stacked configuration, which is easier to construct in modular form and suitable for engineering scale-up and quality consistency control. By dividing the functions of the electrodes / current collectors as electron channels and the electrolyte layer as ion channels, the formation of uncontrolled electron leakage pathways in the electrolyte bulk phase is avoided, which helps to reduce the risk of self-discharge and improve the safety margin of the device.

[0052] Optionally, the electrode layer is a carbon-based electrode layer, and the material is selected from one or more of activated carbon, carbon black, graphite, graphene, and carbon nanotubes.

[0053] Optionally, the current collector is selected from titanium mesh, nickel foam, carbon cloth, conductive polymer film or stainless steel mesh.

[0054] In some embodiments, an interface transition layer is provided between the electrode layer and the structural electrolyte layer, and the interface transition layer is a high-porosity gel thin layer and / or a thin layer containing a liquid-retaining material.

[0055] Understandably, the electrode layer and current collector are responsible for electron transport and charge collection, while the electrolyte layer primarily functions as an ion conductor and provides isolation. Therefore, the conductive components are preferably arranged in the electrode layer / current collector / interface layer, rather than pursuing continuous electron conduction in the electrolyte bulk phase, to avoid the formation of self-discharge paths. To reduce the electrode / electrolyte interface impedance and improve interlayer adhesion, an interface transition layer can be provided between the electrode layer and the electrolyte layer. The transition layer can be a high-porosity cementitious thin layer and / or a thin layer containing liquid-retaining materials, ensuring more sufficient ion supply and more stable contact at the interface, thereby improving device consistency and cycle stability. Optionally, the high-porosity cementitious thin layer is a porous thin layer formed by an alkali-activated cementitious material composed of desulfurized gypsum-slag-steel slag.

[0056] In some embodiments, an alkali-resistant sealing edge structure is provided around the structural supercapacitor energy storage battery to suppress water loss from the structural electrolyte layer.

[0057] A third aspect of the present invention provides a method for preparing the above-described structured supercapacitor energy storage battery, comprising: Desulfurized gypsum, granulated blast furnace slag, and steel slag are dry-mixed according to the above proportions to obtain a gelled solid. The powder activator is added to the gelled solids and dry-mixed to obtain a mixture; wherein the total amount of powder activator is 2% to 15% of the mass of the gelled solids; The liquid-retaining material is pre-loaded with electrolyte until it is saturated with liquid and the surface free liquid is removed before being added to the mixture. Water is then added and mixed to obtain a slurry. The slurry is molded and cured to obtain a structural electrolyte layer; An electrode layer is prepared and combined with a current collector, and a structural electrolyte layer is sandwiched between the two electrode layers to form a stacked structure. The laminated structure is pressed together and the perimeter is sealed with an alkali-resistant seal to obtain a structural supercapacitor energy storage battery.

[0058] The method for preparing a structural supercapacitor energy storage battery provided in this invention includes solid waste grinding and dry mixing, mixing of powder activator and solid waste, preloading electrolyte into liquid-retaining material (immersing until saturated and removing free liquid), adding water and mixing, molding and curing, preparation of electrodes and current collectors, and lamination and encapsulation. The method and timing of preloading electrolyte into the liquid-retaining material are as follows: preferably, the preloading of electrolyte into the liquid-retaining material is completed first, followed by mixing with water and the dry mixture, to avoid excessive water absorption by the liquid-retaining material during the mixing stage, which could cause malfunctions and affect the pore structure.

[0059] In some embodiments, by enriching the liquid-retaining material in the region near the electrode interface and / or providing a highly porous gelled thin layer between the electrode layer and the structural electrolyte layer, the region near the electrode interface has a higher liquid content and / or a lower interfacial impedance.

[0060] A fourth aspect of the present invention provides the application of the above-described structural supercapacitor energy storage battery in building components, prefabricated wall panels, or road components.

[0061] In summary, this invention uses a solid waste alkali-activated cementitious material as the electrolyte carrier framework of the structural supercapacitor. The continuous solid-phase network formed after hardening provides mechanical strength, while ion migration is achieved through interconnected pores and pore solution. Furthermore, a liquid-retaining material is introduced inside the electrolyte layer. When external dryness causes a decrease in pore liquid content, the liquid-retaining material preferentially releases the stored electrolyte, slowing down ion channel contraction and the rapid increase in interfacial impedance, thereby improving the electrochemical stability of the device in non-ideal environments. At the device level, this invention employs a stacked configuration to achieve a division of labor between electron and ion transport paths: electron transport is undertaken by the current collector and electrode layers; ion transport is undertaken by the electrolyte layer, structurally reducing the risks of self-discharge and short circuits.

[0062] Example 1 (I) Preparation of all-solid waste alkali-activated structured electrolyte materials The raw material ratio of the all-solid waste alkali-activated structure electrolyte material in this embodiment is shown in Table 1.

[0063] By weight, 15 parts of desulfurized gypsum (FGD), 60 parts of granulated blast furnace slag (GGBS), and 25 parts of steel slag (SS) are mixed evenly to form the cementitious solids. Na2CO3 and Na2SO4 are mixed at a mass ratio of 9:1 to prepare a powder activator, with a total dosage of 6% of the cementitious solids mass. Superabsorbent polymer (SAP) particles are impregnated in 1.0 M Na2SO4 electrolyte until saturated, and after removing the surface free liquid, they are used as a liquid-retaining material, with a dosage of 0.3% of the cementitious solids mass.

[0064] The above-mentioned gelled solids, powder activator and liquid-retaining material are dry-mixed evenly, water is added and mixed, and then molded. After standard curing, the all-solid waste alkali activated structure electrolyte material is obtained.

[0065] (II) Assembly of Structural Supercapacitor Energy Storage Battery Using the above-mentioned electrolyte materials, the following layers are stacked and assembled in the following order: titanium mesh current collector, carbon black electrode layer, all-solid waste structure electrolyte layer, carbon black electrode layer, and titanium mesh current collector. After pressing, a structural supercapacitor energy storage battery is obtained.

[0066] (III) Performance Testing The performance of the supercapacitor energy storage battery prepared in this embodiment was tested: under the conditions of 25°C and 50% relative humidity, the ionic conductivity was measured to be 5.5 mS / cm and the sheet capacitance was 115 mF / cm. 2 After drying at 25℃ and 40% relative humidity for 7 days, the capacitance retention rate was 70%; the compressive strength was 50 MPa. Specific test results are shown in Table 2.

[0067] Example 2 (I) Preparation of all-solid waste alkali-activated structured electrolyte materials The raw material ratio of the all-solid waste alkali-activated structure electrolyte material in this embodiment is shown in Table 1.

[0068] By weight, 15 parts desulfurized gypsum, 60 parts granulated blast furnace slag, and 25 parts steel slag are mixed evenly to form the cementitious solid. Na₂CO₃ and Na₂SO₄ are mixed at a mass ratio of 9:1 to prepare a powder activator, with a total dosage of 4% of the cementitious solid mass. Superabsorbent resin particles are impregnated in 1.0 M Na₂SO₄ electrolyte until saturated, and after removing surface free liquid, they are used as a liquid-retaining material, with a dosage of 0.3% of the cementitious solid mass.

[0069] The above-mentioned gelled solids, powder activator and liquid-retaining material are dry-mixed evenly, water is added and mixed, and then molded. After standard curing, the all-solid waste alkali activated structure electrolyte material is obtained.

[0070] (II) Assembly of Structural Supercapacitor Energy Storage Battery Using the above-mentioned electrolyte materials, the following layers are stacked and assembled in the following order: titanium mesh current collector, carbon black electrode layer, all-solid waste structure electrolyte layer, carbon black electrode layer, and titanium mesh current collector. After pressing, a structural supercapacitor energy storage battery is obtained.

[0071] (III) Performance Testing The performance of the supercapacitor energy storage battery prepared in this embodiment was tested: under the conditions of 25°C and 50% relative humidity, the ionic conductivity was measured to be 4.7 mS / cm and the sheet capacitance was 105 mF / cm. 2After drying at 25℃ and 40% relative humidity for 7 days, the capacitance retention rate was 66%; the compressive strength was 44 MPa. Specific test results are shown in Table 2.

[0072] Example 3 (I) Preparation of all-solid waste alkali-activated structured electrolyte materials The raw material ratio of the all-solid waste alkali-activated structure electrolyte material in this embodiment is shown in Table 1.

[0073] By weight, 15 parts desulfurized gypsum, 60 parts granulated blast furnace slag, and 25 parts steel slag are mixed evenly to form the cementitious solid. Na₂CO₃ and Na₂SO₄ are mixed at a mass ratio of 9:1 to prepare a powder activator, with a total dosage of 8% of the cementitious solid mass. Superabsorbent resin particles are impregnated in a 1.0 M Na₂SO₄ electrolyte until saturated, and after removing the surface free liquid, they are used as a liquid-retaining material, with a dosage of 0.3% of the cementitious solid mass.

[0074] The above-mentioned gelled solids, powder activator and liquid-retaining material are dry-mixed evenly, water is added and mixed, and then molded. After standard curing, the all-solid waste alkali activated structure electrolyte material is obtained.

[0075] (II) Assembly of Structural Supercapacitor Energy Storage Battery Using the above-mentioned electrolyte materials, the following layers are stacked and assembled in the following order: titanium mesh current collector, carbon black electrode layer, all-solid waste structure electrolyte layer, carbon black electrode layer, and titanium mesh current collector. After pressing, a structural supercapacitor energy storage battery is obtained.

[0076] (III) Performance Testing The performance of the supercapacitor energy storage battery prepared in this embodiment was tested: under the conditions of 25°C and 50% relative humidity, the ionic conductivity was measured to be 6.2 mS / cm and the sheet capacitance was 121 mF / cm. 2 After drying at 25℃ and 40% relative humidity for 7 days, the capacitance retention rate was 72%; the compressive strength was 48 MPa. Specific test results are shown in Table 2.

[0077] Example 4 (I) Preparation of all-solid waste alkali-activated structured electrolyte materials The raw material ratio of the all-solid waste alkali-activated structure electrolyte material in this embodiment is shown in Table 1.

[0078] By weight, 15 parts desulfurized gypsum, 60 parts granulated blast furnace slag, and 25 parts steel slag are mixed evenly to form the cementitious solid. NaOH and Na₂SO₄ are mixed at a mass ratio of 9:1 to prepare a powder activator, with a total dosage of 6% of the cementitious solid mass. Superabsorbent resin particles are impregnated in 1.0 M Na₂SO₄ electrolyte until saturated, and after removing surface free liquid, they are used as a liquid-retaining material, with a dosage of 1.0% of the cementitious solid mass.

[0079] The above-mentioned gelled solids, powder activator and liquid-retaining material are dry-mixed evenly, water is added and mixed, and then molded. After standard curing, the all-solid waste alkali activated structure electrolyte material is obtained.

[0080] (II) Assembly of Structural Supercapacitor Energy Storage Battery Using the above-mentioned electrolyte materials, the following layers are stacked and assembled in the following order: titanium mesh current collector, carbon black electrode layer, all-solid waste structure electrolyte layer, carbon black electrode layer, and titanium mesh current collector. After pressing, a structural supercapacitor energy storage battery is obtained.

[0081] (III) Performance Testing The performance of the supercapacitor energy storage battery prepared in this embodiment was tested: under the conditions of 25°C and 50% relative humidity, the ionic conductivity was measured to be 9.3 mS / cm and the sheet capacitance was 133 mF / cm. 2 After drying at 25℃ and 40% relative humidity for 7 days, the capacitance retention rate was 72%; the compressive strength was 43 MPa. Specific test results are shown in Table 2.

[0082] Example 5 (I) Preparation of all-solid waste alkali-activated structured electrolyte materials The raw material ratio of the all-solid waste alkali-activated structure electrolyte material in this embodiment is shown in Table 1.

[0083] By weight, 25 parts of desulfurized gypsum, 55 parts of granulated blast furnace slag, and 20 parts of steel slag are mixed evenly to form the cementitious solid. Na₂CO₃ and Na₂SO₄ are mixed at a mass ratio of 9:1 to prepare a powder activator, with a total dosage of 6% of the cementitious solid mass. In this embodiment, a composite liquid-retaining material is used: superabsorbent resin particles are impregnated in 1.0 M Na₂SO₄ electrolyte until saturated, and after removing the surface free liquid, this is used as liquid-retaining material A, with a dosage of 0.5% of the cementitious solid mass; zeolite particles are impregnated in 1.0 M Na₂SO₄ electrolyte until adsorption saturated, and after removing the surface free liquid, this is used as liquid-retaining material B, with a dosage of 3% of the cementitious solid mass.

[0084] The above-mentioned gelled solids, powder activator, and liquid-retaining materials A and B are dry-mixed evenly, and water is added and mixed to form a solid material. After standard curing, the all-solid waste alkali activated structure electrolyte material is obtained.

[0085] (II) Assembly of Structural Supercapacitor Energy Storage Battery Using the above-mentioned electrolyte materials, the following layers are stacked and assembled in the following order: titanium mesh current collector, carbon black electrode layer, all-solid waste structure electrolyte layer, carbon black electrode layer, and titanium mesh current collector. After pressing, a structural supercapacitor energy storage battery is obtained.

[0086] (III) Performance Testing The performance of the supercapacitor energy storage battery prepared in this embodiment was tested: under the conditions of 25°C and 50% relative humidity, the ionic conductivity was measured to be 8.6 mS / cm and the sheet capacitance was 126 mF / cm. 2 After drying at 25℃ and 40% relative humidity for 7 days, the capacitance retention rate was 79%; the compressive strength was 45 MPa. Specific test results are shown in Table 2.

[0087] Example 6 (I) Preparation of all-solid waste alkali-activated structured electrolyte materials The raw material ratio of the all-solid waste alkali-activated structure electrolyte material in this embodiment is shown in Table 1.

[0088] By weight, 15 parts of desulfurized gypsum, 50 parts of granulated blast furnace slag, and 35 parts of steel slag are mixed evenly to form the cementitious solid. NaOH and Na₂SO₄ are mixed at a mass ratio of 9:1 to prepare a powder activator, with a total dosage of 6% of the cementitious solid mass. Superabsorbent resin particles are impregnated in 1.0 M Na₂SO₄ electrolyte until saturated, and after removing surface free liquid, they are used as a liquid-retaining material, with a dosage of 0.3% of the cementitious solid mass.

[0089] In this embodiment, the liquid-retaining material is formed by layering during molding, creating a gradient distribution in the thickness direction of the electrolyte layer. The liquid-retaining material content is higher in the region near the electrode interface than in the central bearing region.

[0090] The above-mentioned gelled solids, powder activator and liquid retention material are dry mixed evenly, and water is added and mixed. The mixture is then formed by layering and spreading the material. After standard curing, the all-solid waste alkali activated structure electrolyte material is obtained.

[0091] (II) Assembly of Structural Supercapacitor Energy Storage Battery Using the above-mentioned electrolyte materials, the following layers are stacked and assembled in the following order: titanium mesh current collector, carbon black electrode layer, all-solid waste structure electrolyte layer, carbon black electrode layer, and titanium mesh current collector. After pressing, a structural supercapacitor energy storage battery is obtained.

[0092] (III) Performance Testing The performance of the supercapacitor energy storage battery prepared in this embodiment was tested: under the conditions of 25°C and 50% relative humidity, the ionic conductivity was measured to be 8.8 mS / cm and the sheet capacitance was 128 mF / cm.2 After drying at 25℃ and 40% relative humidity for 7 days, the capacitance retention rate was 81%; the compressive strength was 49 MPa. Specific test results are shown in Table 2.

[0093] Example 7 (I) Preparation of all-solid waste alkali-activated structured electrolyte materials The raw material ratio of the all-solid waste alkali-activated structure electrolyte material in this embodiment is shown in Table 1.

[0094] By weight, 15 parts desulfurized gypsum, 60 parts granulated blast furnace slag, and 25 parts steel slag are mixed evenly to form the cementitious solid. NaOH and Na₂SO₄ are mixed at a mass ratio of 9:1 to prepare a powder activator, with a total dosage of 8% of the cementitious solid mass. Superabsorbent resin particles are impregnated in 1.0 M Na₂SO₄ electrolyte until saturated, and after removing surface free liquid, they are used as a liquid-retaining material, with a dosage of 0.3% of the cementitious solid mass.

[0095] The above-mentioned gelled solids, powder activator and liquid-retaining material are dry-mixed evenly, water is added and mixed, and then molded. After standard curing, the all-solid waste alkali activated structure electrolyte material is obtained.

[0096] (II) Assembly of Structural Supercapacitor Energy Storage Battery Using the above-mentioned electrolyte materials, the layers are stacked and assembled in the following order: titanium mesh current collector, carbon black electrode layer, all-solid waste structure electrolyte layer, carbon black electrode layer, and titanium mesh current collector. After pressing, a structural supercapacitor energy storage battery is obtained. After assembly, an alkali-resistant sealing edge structure is set on the side of the device.

[0097] (III) Performance Testing The performance of the supercapacitor energy storage battery prepared in this embodiment was tested: under the conditions of 25°C and 50% relative humidity, the ionic conductivity was measured to be 9.0 mS / cm and the sheet capacitance was 130 mF / cm. 2 After drying at 25℃ and 40% relative humidity for 7 days, the capacitance retention rate was 85%; the compressive strength was 47 MPa. Specific test results are shown in Table 2.

[0098] Comparative Example 1 (I) Preparation of all-solid waste alkali-activated structured electrolyte materials The raw material ratios of the all-solid waste alkali-activated structure electrolyte material in this comparative example are shown in Table 1.

[0099] By weight, 15 parts desulfurized gypsum, 60 parts granulated blast furnace slag, and 25 parts steel slag were mixed evenly to form the cementitious solid. Na₂CO₃ and Na₂SO₄ were mixed at a mass ratio of 9:1 to prepare a powder activator, the total dosage of which was 6% of the mass of the cementitious solid. No liquid-retaining materials were added in this comparative example.

[0100] The above-mentioned gelled solids and powder activator are dry-mixed evenly, water is added and mixed, and then shaped. After standard curing, the all-solid waste alkali activated structure electrolyte material is obtained.

[0101] (II) Assembly of Structural Supercapacitor Energy Storage Battery Using the above-mentioned electrolyte materials, the following layers are stacked and assembled in the following order: titanium mesh current collector, carbon black electrode layer, all-solid waste structure electrolyte layer, carbon black electrode layer, and titanium mesh current collector. After pressing, a structural supercapacitor energy storage battery is obtained.

[0102] (III) Performance Testing The performance of the supercapacitor energy storage battery prepared in this comparative example was tested: under the conditions of 25℃ and 50% relative humidity, the ionic conductivity was measured to be 3.9 mS / cm and the sheet capacitance was 95 mF / cm. 2 After drying at 25℃ and 40% relative humidity for 7 days, the capacitance retention rate was 40%; the compressive strength was 52 MPa. Specific test results are shown in Table 2.

[0103] Comparative Example 2 (I) Preparation of all-solid waste alkali-activated structured electrolyte materials The raw material ratios of the all-solid waste alkali-activated structure electrolyte material in this comparative example are shown in Table 1.

[0104] By weight, 15 parts desulfurized gypsum, 60 parts granulated blast furnace slag, and 25 parts steel slag were mixed evenly to form the cementitious solid. NaOH and Na₂SO₄ were mixed at a mass ratio of 9:1 to prepare a powder activator, the total dosage of which was 6% of the cementitious solid mass. No liquid-retaining materials were added in this comparative example.

[0105] The above-mentioned gelled solids and powder activator are dry-mixed evenly, water is added and mixed, and then shaped. After standard curing, the all-solid waste alkali activated structure electrolyte material is obtained.

[0106] (II) Assembly of Structural Supercapacitor Energy Storage Battery Using the above-mentioned electrolyte materials, the following layers are stacked and assembled in the following order: titanium mesh current collector, carbon black electrode layer, all-solid waste structure electrolyte layer, carbon black electrode layer, and titanium mesh current collector. After pressing, a structural supercapacitor energy storage battery is obtained.

[0107] (III) Performance Testing The performance of the supercapacitor energy storage battery prepared in this comparative example was tested: under the conditions of 25℃ and 50% relative humidity, the ionic conductivity was measured to be 4.8 mS / cm and the sheet capacitance was 102 mF / cm. 2 After drying at 25℃ and 40% relative humidity for 7 days, the capacitance retention rate was 38%; the compressive strength was 55 MPa. Specific test results are shown in Table 2.

[0108] Comparative Example 3 (I) Preparation of all-solid waste alkali-activated structured electrolyte materials The raw material ratios of the all-solid waste alkali-activated structure electrolyte material in this comparative example are shown in Table 1.

[0109] By weight, 15 parts desulfurized gypsum, 60 parts granulated blast furnace slag, and 25 parts steel slag were mixed evenly to form the cementitious solid. Na₂CO₃ and Na₂SO₄ were mixed at a mass ratio of 9:1 to prepare a powder activator, the total dosage of which was 4% of the mass of the cementitious solid. No liquid-retaining materials were added in this comparative example.

[0110] The above-mentioned gelled solids and powder activator are dry-mixed evenly, water is added and mixed, and then shaped. After standard curing, the all-solid waste alkali activated structure electrolyte material is obtained.

[0111] (II) Assembly of Structural Supercapacitor Energy Storage Battery Using the above-mentioned electrolyte materials, the following layers are stacked and assembled in the following order: titanium mesh current collector, carbon black electrode layer, all-solid waste structure electrolyte layer, carbon black electrode layer, and titanium mesh current collector. After pressing, a structural supercapacitor energy storage battery is obtained.

[0112] (III) Performance Testing The performance of the supercapacitor energy storage battery prepared in this comparative example was tested: under the conditions of 25℃ and 50% relative humidity, the ionic conductivity was measured to be 3.1 mS / cm and the sheet capacitance was 82 mF / cm. 2 After drying at 25℃ and 40% relative humidity for 7 days, the capacitance retention rate was 35%; the compressive strength was 45 MPa. Specific test results are shown in Table 2.

[0113] Comparative Example 4 (I) Preparation of all-solid waste alkali-activated structured electrolyte materials The raw material ratios of the all-solid waste alkali-activated structure electrolyte material in this comparative example are shown in Table 1.

[0114] By weight, 15 parts desulfurized gypsum, 60 parts granulated blast furnace slag, and 25 parts steel slag were mixed evenly to form the cementitious solid. Na₂CO₃ and Na₂SO₄ were mixed at a mass ratio of 9:1 to prepare a powder activator, the total dosage of which was 8% of the mass of the cementitious solid. No liquid-retaining materials were added in this comparative example.

[0115] The above-mentioned gelled solids and powder activator are dry-mixed evenly, water is added and mixed, and then shaped. After standard curing, the all-solid waste alkali activated structure electrolyte material is obtained.

[0116] (II) Assembly of Structural Supercapacitor Energy Storage Battery Using the above-mentioned electrolyte materials, the following layers are stacked and assembled in the following order: titanium mesh current collector, carbon black electrode layer, all-solid waste structure electrolyte layer, carbon black electrode layer, and titanium mesh current collector. After pressing, a structural supercapacitor energy storage battery is obtained.

[0117] (III) Performance Testing The performance of the supercapacitor energy storage battery prepared in this comparative example was tested: under the conditions of 25℃ and 50% relative humidity, the ionic conductivity was measured to be 4.2 mS / cm and the sheet capacitance was 98 mF / cm. 2 After drying at 25℃ and 40% relative humidity for 7 days, the capacitance retention rate was 37%; the compressive strength was 50 MPa. Specific test results are shown in Table 2.

[0118] Comparative Example 5 (I) Preparation of all-solid waste alkali-activated structured electrolyte materials The raw material ratios of the all-solid waste alkali-activated structure electrolyte material in this comparative example are shown in Table 1.

[0119] By weight, 15 parts desulfurized gypsum, 60 parts granulated blast furnace slag, and 25 parts steel slag are mixed evenly to form the cementitious solids. Na₂CO₃ and Na₂SO₄ are mixed at a mass ratio of 9:1 to prepare a powder activator, with a total dosage of 6% of the cementitious solids mass. Superabsorbent resin particles (without pre-loaded electrolyte) are used as a liquid-retaining material, with a dosage of 1.0% of the cementitious solids mass.

[0120] The above-mentioned gelled solids, powder activator and liquid-retaining material are dry-mixed evenly, water is added and mixed, and then molded. After standard curing, the all-solid waste alkali activated structure electrolyte material is obtained.

[0121] (II) Assembly of Structural Supercapacitor Energy Storage Battery Using the above-mentioned electrolyte materials, the following layers are stacked and assembled in the following order: titanium mesh current collector, carbon black electrode layer, all-solid waste structure electrolyte layer, carbon black electrode layer, and titanium mesh current collector. After pressing, a structural supercapacitor energy storage battery is obtained.

[0122] (III) Performance Testing The performance of the supercapacitor energy storage battery prepared in this comparative example was tested: under the conditions of 25℃ and 50% relative humidity, the ionic conductivity was measured to be 5.0 mS / cm and the sheet capacitance was 108 mF / cm. 2 After drying for 7 days at 25℃ and 40% relative humidity, the capacitance retention rate was 52%; the compressive strength was 47 MPa. Specific test results are shown in Table 2.

[0123] Comparative Example 6 (I) Preparation of all-solid waste alkali-activated structured electrolyte materials The raw material ratios of the all-solid waste alkali-activated structure electrolyte material in this comparative example are shown in Table 1.

[0124] By weight, take 15 parts desulfurized gypsum, 60 parts granulated blast furnace slag, and 25 parts steel slag, and mix them evenly to form the cementitious solid. Mix NaOH and Na2SO4 at a mass ratio of 1:1 to prepare a powder activator, the total dosage of which is 6% of the mass of the cementitious solid. No liquid-retaining materials are added in this comparative example.

[0125] The above-mentioned gelled solids and powder activator are dry-mixed evenly, water is added and mixed, and then shaped. After standard curing, the all-solid waste alkali activated structure electrolyte material is obtained.

[0126] (II) Assembly of Structural Supercapacitor Energy Storage Battery Using the above-mentioned electrolyte materials, the following layers are stacked and assembled in the following order: titanium mesh current collector, carbon black electrode layer, all-solid waste structure electrolyte layer, carbon black electrode layer, and titanium mesh current collector. After pressing, a structural supercapacitor energy storage battery is obtained.

[0127] (III) Performance Testing The performance of the supercapacitor energy storage battery prepared in this comparative example was tested: under the conditions of 25℃ and 50% relative humidity, the ionic conductivity was measured to be 4.3 mS / cm and the sheet capacitance was 99 mF / cm. 2 After drying at 25℃ and 40% relative humidity for 7 days, the capacitance retention rate was 40%; the compressive strength was 54 MPa. Specific test results are shown in Table 2.

[0128] Comparative Example 7 (I) Preparation of all-solid waste alkali-activated structured electrolyte materials The raw material ratios of the all-solid waste alkali-activated structure electrolyte material in this comparative example are shown in Table 1.

[0129] By weight, 15 parts desulfurized gypsum, 60 parts granulated blast furnace slag, and 25 parts steel slag are mixed evenly to form the cementitious solid. Na₂CO₃ and Na₂SO₄ are mixed at a mass ratio of 1:9 to prepare a powder activator, with a total dosage of 6% of the cementitious solid mass. No liquid-retaining materials are added in this comparative example.

[0130] The above-mentioned gelled solids and powder activator are dry-mixed evenly, water is added and mixed, and then shaped. After standard curing, the all-solid waste alkali activated structure electrolyte material is obtained.

[0131] (II) Assembly of Structural Supercapacitor Energy Storage Battery Using the above-mentioned electrolyte materials, the following layers are stacked and assembled in the following order: titanium mesh current collector, carbon black electrode layer, all-solid waste structure electrolyte layer, carbon black electrode layer, and titanium mesh current collector. After pressing, a structural supercapacitor energy storage battery is obtained.

[0132] (III) Performance Testing The performance of the supercapacitor energy storage battery prepared in this comparative example was tested: under the conditions of 25℃ and 50% relative humidity, the ionic conductivity was measured to be 3.4 mS / cm and the sheet capacitance was 88 mF / cm. 2 After drying at 25℃ and 40% relative humidity for 7 days, the capacitance retention rate was 42%; the compressive strength was 56 MPa. Specific test results are shown in Table 2.

[0133] Table 1. Raw material formulation of the structural electrolyte materials in the examples and comparative examples.

[0134] Table 2 Performance test results of the supercapacitor energy storage batteries in the examples and comparative examples

[0135] In Table 2: Ionic conductivity (σ, mS / cm): the magnitude of ion conduction ability in the electrolyte material; the higher the value, the easier ion migration and the lower the internal resistance; unit: millisiemens / cm (mS / cm). Sheet capacitance ( C , mF / cm 2 ): Capacitance value normalized to the effective electrode area, used to compare the energy storage capacity of devices of different sizes; unit: millifarads per square centimeter (mF / cm²) 2 Capacitance retention rate (%, after 7 days of drying, 25℃, RH 40% drying): The percentage of the surface capacitance retained relative to the initial value after the sample has been placed under specified drying conditions for 7 days; retention rate = surface capacitance after 7 days of drying / initial surface capacitance × 100%. Compressive strength ( f c (MPa): The compressive strength of the electrolyte material as a load-bearing cementitious skeleton; unit: megapascal (MPa).

[0136] Results Analysis Overall, as shown in Table 2 / Figure 1-4 As can be seen, the system of the present invention exhibits significant differences in ionic conductivity σ, surface capacitance C, capacitance retention rate after 7 days of drying, and compressive strength under different activation systems, activator dosages, liquid-retaining material forms, and structural designs. The most critical technical effect is that, after introducing a pre-loaded electrolyte liquid-retaining material, the capacitance retention rate under drying conditions significantly increases from approximately 35%–52% in the comparative example to 70%–85%, while maintaining high ionic conductivity and surface capacitance, and still maintaining an engineering-usable compressive strength level. This indicates that the all-solid waste alkali-activated carrier electrolyte framework proposed in this application, matched with a liquid-retaining material (optional gradient / interface and sealing), significantly contributes to suppressing drying degradation. The main embodiments and comparative examples are discussed below: 1) Comparative examples, primarily by changing the excitation system / dosage, are insufficient to address drying degradation. Comparative Examples 1-4 mainly examine the impact of excitation system type and dosage on performance under conditions without liquid retention materials. Comparative Example 3 (dosage 4%) shows significantly lower ionic conductivity σ and areal capacitance, as well as lower compressive strength, indicating that insufficient excitation dosing weakens the reaction degree and pore solution ionic strength, limiting ion transport and interfacial kinetics. Comparative Example 4 (dosage 8%) shows only limited improvement in σ and areal capacitance compared to Comparative Example 1 (dosage 6%), but the 7-day drying retention rate does not improve synchronously and remains at a low level, indicating that simply increasing the excitation dosage or initial ionic strength cannot fundamentally suppress ion channel degradation and interfacial impedance growth caused by drying dehydration. Comparative Example 2 (enhanced excitation system), while improving σ and areal capacitance compared to Comparative Example 1, still shows a low 7-day drying retention rate, and the changes do not exhibit a monotonic relationship of improvement with increasing alkalinity. This further demonstrates that, without a retaining agent, capacitor performance in a dry environment is primarily limited by the electrolyte content and ion channel continuity, rather than solely by initial alkalinity or salt concentration. Comparative Example 6 / 7 (with internal activator ratio supplementation) illustrates how changes in powder ratio can cause differences in σ and areal capacitance; however, under conditions without a retaining agent or sealing, the dryness retention rate still falls short of the levels of the Example group. This result indicates that optimizing the activator system ratio can improve initial conduction and interfacial reactions, but it cannot replace the role of a retaining agent in resisting drying.

[0137] 2) The electrolyte-preloaded liquid-retaining material is crucial for the supercapacitor energy storage battery structure of this invention. Comparative Example 5 (1.0% SAP but without preloaded electrolyte) showed improvements in σ, sheet capacitance, and dryness retention compared to Comparative Example 1 (without SAP), indicating that SAP, as an internal maintenance / water-retaining component, can improve the liquid content and the continuity of ion migration to a certain extent. However, the dryness retention rate of Comparative Example 5 was still significantly lower than that of the Example Group (preloaded electrolyte liquid-retaining material), indicating that SAP alone is insufficient to maintain the ionic strength and interfacial stability of the pore solution under dry conditions for a long period. In Examples 1-3, under the same solid waste baseline ratio, using 0.3% SAP preloaded Na2SO4 electrolyte, even with variations in activator dosage from 4% to 8%, the dryness retention rate consistently increased to approximately 66% to 72%, and σ and sheet capacitance also increased accordingly. This indicates that the liquid-retaining material preloaded with electrolyte can simultaneously provide moisture buffering and ion replenishment, which can significantly slow down the ion channel breakage and interfacial impedance rise caused by drying. This is an important technical feature that distinguishes this application from the prior art.

[0138] 3) Further, it is necessary to improve the resistance to drying through engineering structural design. Example 7, based on the pre-loaded electrolyte retention material, further employs an interface transition layer and edge sealing design, increasing the 7-day retention rate to approximately 85%, the highest level in the entire system. This result indicates that in practical engineering environments, electrolyte boundary water loss is often a rapid channel for performance degradation; by suppressing edge water loss through edge sealing and maintaining a more stable liquid content and ion supply at the electrode / electrolyte interface through the interface transition layer, the rate of interface impedance growth can be significantly reduced, thereby achieving higher drying stability. In addition, Example 6 uses a gradient enrichment method with SAP pre-loaded electrolyte, resulting in a higher content of electrolyte retention material near the electrode interface and a relatively lower content in the central support zone. This partitioned arrangement balances interface ion supply and structural support, which helps maintain high surface capacitance and high σ while avoiding uncontrolled electron leakage channels in the electrolyte bulk phase, structurally reducing the risk of self-discharge.

[0139] 4) The inherent benefits of the solid waste materials are crucial. Example 5 (FGD increased and using SAP+zeolite composite liquid-retaining material) showed improved dryness retention rate compared to the baseline example, while maintaining high σ and areal capacitance. This indicates that appropriately increasing sulfate supply and using liquid-retaining materials helps create a more stable porous solution ionic environment and liquid content buffering mechanism. Example 6 (steel slag increased) maintained high levels in σ, areal capacitance, and dryness retention rate, while compressive strength remained within the engineering-usable range. This suggests that while steel slag acts as a calcium source / filler phase in forming the load-bearing framework, its iron content (e.g., Fe²⁺) also contributes to the formation of the load-bearing framework. + / Fe³ + Oxide or iron-phase particles may have a certain promoting effect on electrochemical interfacial processes: on the one hand, the presence of iron phase may provide more polarizable / active sites for pseudocapacitive processes at the electrode / electrolyte interface, thereby helping to improve the surface capacitance; on the other hand, some iron-phase particles in steel slag may also improve the microscopic pathways of local electron / ion transport, making the interfacial charge transfer more complete. It should be noted that this application does not use iron phase as the only mechanism, but experimental results show that with reasonable proportioning and structural design (such as gradient enrichment and interfacial transition layer), the multiphase components (including Fe-related phases) brought by steel slag may have a synergistic effect on device performance improvement, reflecting the potential added value of the all-solid waste system in the direction of energy storage materials.

[0140] It will be readily understood by those skilled in the art that the above-described advantageous methods can be freely combined and superimposed without conflict. The above are merely preferred embodiments of this application and are not intended to limit this application. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application should be included within the protection scope of this application. The above are merely preferred embodiments of this application. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of this application, and these improvements and modifications should also be considered within the protection scope of this application.

Claims

1. A solid waste-based electrolyte, characterized in that, include: Cementitious solids, powder activators, and liquid-retaining materials; among which, The cementitious solids, by weight, include: 5-35 parts of desulfurized gypsum, 30-80 parts of granulated blast furnace slag, and 10-60 parts of steel slag; The powder activator comprises: an alkaline compound and a sulfate, and the dosage of the powder activator is 2% to 15% of the mass of the gel solids; The liquid-retaining material is pre-loaded with electrolyte and has the ability to reversibly absorb and release electrolyte. The amount of the liquid-retaining material is 0.05% to 10% of the mass of the gel solid.

2. The solid waste-based structural electrolyte according to claim 1, characterized in that, The cementitious solids also include at least one of silica fume, fly ash and metakaolin, and the total amount of silica fume, fly ash and metakaolin is 0 to 20 parts by mass.

3. The solid waste-based structural electrolyte according to claim 1, characterized in that, The amount of the powder activator is 4% to 8% of the mass of the gelled solids.

4. The solid waste-based structural electrolyte according to claim 1, characterized in that, The alkaline compound is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; the sulfate is sodium sulfate and / or potassium sulfate.

5. The solid waste-based structural electrolyte according to claim 4, characterized in that, The mass ratio of the alkaline compound to the sulfate is 9:1 to 1:

9.

6. The solid waste-based structural electrolyte according to claim 5, characterized in that, The powder activator is a powder composed of sodium hydroxide and sulfate, a powder composed of a premix of sodium hydroxide and inert filler and sulfate, or a powder composed of a premix of sodium hydroxide and soluble salt and sulfate.

7. The solid waste-based structured electrolyte according to claim 1 or 4, characterized in that, The solid waste-based electrolyte was subjected to water extraction at a solid-liquid ratio of 1:5 to 1:20, and the pH of the resulting extract was in the range of 11.5 to 13.

5.

8. The solid waste-based structural electrolyte according to claim 1, characterized in that, The liquid-retaining material is selected from one or more of the following: Superabsorbent resin particles, with an admixture amount of 0.05% to 2.0% of the mass of the gelled solids; Hydrogel microspheres or microcapsules, at a dosage of 0.1% to 5.0% of the mass of the gelled solids; Porous carrier particles, wherein the porous carrier particles are bentonite, zeolite and / or biochar, and the dosage is 0.5% to 10% of the mass of the cementitious solids.

9. The solid waste-based structural electrolyte according to claim 1 or 8, characterized in that, The electrolyte pre-loaded in the liquid-retaining material is an aqueous solution of at least one salt selected from sodium sulfate, potassium sulfate, sodium chloride, and potassium chloride, or a mixed aqueous solution of several of these salts; wherein the concentration of the pre-loaded electrolyte is 0.5 M to 2 M.

10. The solid waste-based structural electrolyte according to claim 1, characterized in that, The liquid-retaining material is immersed in the electrolyte until it becomes saturated with the liquid and the surface free liquid is removed.

11. The solid waste-based structural electrolyte according to claim 1 or 8, characterized in that, The liquid-retaining material is distributed in a gradient along the thickness direction of the solid waste-based electrolyte, wherein the content of the liquid-retaining material is higher in the region near the electrode interface than in the region far from the electrode interface.

12. A supercapacitor energy storage battery with a specific structure, characterized in that, The structured supercapacitor energy storage battery has a stacked configuration, including: a first current collector, a first electrode layer, a structural electrolyte layer, a second electrode layer, and a second current collector; The structured electrolyte layer adopts the solid waste-based structured electrolyte as described in any one of claims 1-11.

13. The supercapacitor energy storage battery according to claim 12, characterized in that, The electrode layer is a carbon-based electrode layer, and its material is selected from one or more of activated carbon, carbon black, graphite, graphene, and carbon nanotubes.

14. The supercapacitor energy storage battery according to claim 12, characterized in that, The current collector is selected from titanium mesh, nickel foam, carbon cloth, conductive polymer film or stainless steel mesh.

15. The supercapacitor energy storage battery according to claim 12, characterized in that, An interface transition layer is provided between the electrode layer and the structural electrolyte layer. The interface transition layer is a high-porosity gelled thin layer and / or a thin layer containing the liquid-retaining material.

16. The supercapacitor energy storage battery according to claim 12, characterized in that, The supercapacitor energy storage battery has an alkali-resistant sealing edge structure around its perimeter to suppress water loss from the electrolyte layer.

17. A method for preparing a structural supercapacitor energy storage battery, characterized in that, The method for preparing the supercapacitor energy storage battery with the structure according to any one of claims 12-16 includes: The desulfurized gypsum, the granulated blast furnace slag and the steel slag are dry-mixed according to the mass fractions specified in any one of claims 1-11 to obtain the gelled solid. The powder activator is added to the gelled solid and dry-mixed to obtain a mixture; wherein the total amount of the powder activator is 2% to 15% of the mass of the gelled solid; The liquid-retaining material is pre-loaded with electrolyte until it is saturated with liquid and the surface free liquid is removed before being added to the mixture. Water is then added and stirred to obtain a slurry. The slurry is molded and cured to obtain a structural electrolyte layer; An electrode layer is prepared and combined with a current collector, and the electrolyte layer is sandwiched between the two electrode layers to form a stacked structure. The stacked structure is pressed together and the periphery is sealed with an alkali-resistant seal to obtain the supercapacitor energy storage battery structure.

18. The preparation method according to claim 17, characterized in that, By enriching the liquid-retaining material in the region near the electrode interface, and / or by providing the high-porosity gel layer between the electrode layer and the structural electrolyte layer, the region near the electrode interface can have a higher liquid content and / or a lower interfacial impedance.

19. The application of the structural supercapacitor energy storage battery according to any one of claims 12-16 or the structural supercapacitor energy storage battery prepared by the preparation method according to any one of claims 17-18 in building components, prefabricated wall panels or road components.

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