Cement-based energy storage device, power supply system and energy storage building

Abstract

The utility model relates to the technical field of cement-based batteries, in particular to a cement-based energy storage device, a power supply system and an energy storage building. The lithium ion battery comprises a cathode pole piece, an anode pole piece and a cement-based electrolyte matrix, the cathode pole piece is connected with an anode current collector, the anode pole piece is connected with a cathode current collector, the cement-based electrolyte matrix is arranged between the cathode pole piece and the anode pole piece, the distance between the anode current collector and the cathode current collector is 1-3 cm, and the cement-based electrolyte matrix is arranged between the cathode pole piece and the anode pole piece. The distance between the positive current collector and the negative current collector of the cement-based energy storage device is 1-3cm, and the cement-based energy storage device has relatively good current density and current efficiency.

Description

Technical Field

[0001] The utility model relates to the technical field of cement-based battery, and particularly relates to a cement-based energy storage device, a power supply system and an energy storage building. Background Art

[0002] The cement-based electrochemical energy storage technology uses solid cement-based materials as the electrolyte of the battery.

[0003] Making the cement-based material into an energy storage device can provide emergency power in the case of power interruption in extreme weather, such as meeting the needs of lighting and communication, and enhancing the disaster tolerance ability of buildings in the case of power interruption caused by disasters. On the other hand, the future development direction of buildings must be intelligent, endowing buildings with the ability of self-perception and self-regulation. If the cement-based material can provide electric energy, it means that more sensors can be buried inside the concrete to solve its power supply problem.

[0004] The cement-based battery is currently still in the research stage, and there is still a need to improve its performance. Summary of the Utility Model

[0005] The main purpose of the utility model is to propose a cement-based energy storage device, aiming to improve the performance of the cement-based energy storage device.

[0006] To achieve the above purpose, the cement-based energy storage device proposed by the utility model includes:

[0007] A cathode plate, which is connected to the positive current collector;

[0008] An anode plate, which is connected to the negative current collector;

[0009] And a cement-based electrolyte matrix, the cement-based electrolyte matrix is provided between the cathode plate and the anode plate, and the distance between the positive current collector and the negative current collector is 1 cm to 3 cm.

[0010] It can be understood that the distance between the positive current collector and the negative current collector is generally considered that the electrode spacing will affect the current density and current efficiency of the battery. Generally speaking, the smaller the electrode spacing, the higher the current density, the higher the current efficiency, and the better the performance of the battery. However, the electrode spacing cannot be too small, otherwise it will increase the internal resistance of the battery, resulting in voltage drop, and even electrode breakdown, causing damage or safety hazards to the battery. Therefore, the selection of the electrode spacing needs to balance the performance and safety of the battery. In this application, the distance between the positive current collector and the negative current collector is 1 cm to 3 cm, and the cement-based energy storage device has better current density and current efficiency in this range.

[0011] Optionally, the sizes of the positive current collector and the negative current collector are 60 mm × 30 mm × 0.5 mm.

[0012] Optionally, the distance between the anode electrode and the cathode electrode is 10 mm.

[0013] Optionally, the size of the cement-based energy storage device is 50 mm × 50 mm × 78 mm.

[0014] Optionally, at least one of the following conditions is satisfied:

[0015] The active material layer of the cathode electrode includes MnO2, and the anode electrode includes a zinc sheet;

[0016] The cathode electrode includes a copper sheet, and the anode electrode includes a magnesium sheet.

[0017] Optionally, at least one of the following conditions is satisfied:

[0018] The negative current collector includes any one of a zinc sheet, AZ31 magnesium alloy, AZ91 magnesium alloy, 80-mesh AZ91 magnesium alloy mesh, aluminum sheet, aluminum mesh, iron sheet, and iron mesh;

[0019] The positive current collector includes any one of carbon fiber, copper sheet, nickel mesh, nickel sheet, and nickel foam.

[0020] Optionally, the carbon fiber includes polyacrylonitrile-based carbon fiber or polyacrylonitrile-based carbon fiber with a 10-mm mesh.

[0021] Optionally, the active material layer of the cathode electrode includes MnO2, and the size of the active material layer is 25 mm × 50 mm × 78 mm.

[0022] This application also provides a power supply system, which is composed of a plurality of cement-based energy storage devices connected in series and / or in parallel, and the cement-based energy storage device includes the cement-based energy storage device as described above.

[0023] This application also provides an energy storage building, which includes the cement-based energy storage device as described above.

[0024] The cement-based energy storage device includes a cathode electrode, an anode electrode, and a cement-based electrolyte matrix. The cathode electrode is connected to the positive current collector, and the anode electrode is connected to the negative current collector. A cement-based electrolyte matrix is provided between the cathode electrode and the anode electrode. The distance between the positive current collector and the negative current collector is 1 cm to 3 cm. It can be understood that the distance between the positive current collector and the negative current collector, generally considered as the electrode spacing, will affect the current density and current efficiency of the battery. Generally speaking, the smaller the electrode spacing, the higher the current density, the higher the current efficiency, and the better the performance of the battery. However, the electrode spacing cannot be too small, otherwise it will increase the internal resistance of the battery, resulting in a voltage drop, and even electrode breakdown, causing damage or safety hazards to the battery. Therefore, the selection of the electrode spacing needs to balance the performance and safety of the battery. In this application, the distance between the positive current collector and the negative current collector is 1 cm to 3 cm, and under this range, the cement-based energy storage device has better current density and current efficiency. Description of the Drawings

[0025] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on the structures shown in these drawings.

[0026] Figure 1 It is a schematic structural diagram of a cement-based energy storage device provided by the present invention;

[0027] Figure 2 It is the battery discharge external circuit voltage diagram in Embodiments 1 to 3 of the present invention;

[0028] Figure 3 It is the battery discharge external circuit voltage-time diagram in Embodiments 4 to 6 of the present invention;

[0029] Figure 4 It is the battery discharge external circuit voltage-time diagram in Embodiments 7 to 9 of the present invention;

[0030] Figure 5 It is the battery discharge voltage-time diagram in Embodiments 7, 8 and 10, 11 of the present invention;

[0031] Figure 6 It is the battery discharge voltage-time diagram in Embodiment 12 of the present invention;

[0032] Figure 7 It is the battery discharge voltage-time diagram in Embodiment 13 of the present invention;

[0033] Figure 8It is the battery discharge voltage-time graph in Embodiment 14 of the present utility model;

[0034] Figure 9 It is the battery discharge voltage-time graph in Embodiment 15 of the present utility model.

[0035] Explanation of the attached drawing reference numerals:

[0036] 1. Cement-based electrolyte matrix; 2. Positive current collector; 3. Negative current collector.

[0037] The realization, functional features and advantages of the purpose of the present utility model will be further described with reference to the embodiments and the attached drawings. Specific embodiments

[0038] Next, the technical solutions in the embodiments of the present utility model will be clearly and completely described with reference to the attached drawings in the embodiments of the present utility model. Obviously, the described embodiments are only a part of the embodiments of the present utility model, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present utility model without creative work belong to the scope of protection of the present utility model.

[0039] It should be noted that if there are directional indications (such as up, down, left, right, front, back...) involved in the embodiments of the present utility model, the directional indications are only used to explain the relative positional relationship and movement conditions between components in a specific posture. If the specific posture changes, the directional indications will also change accordingly.

[0040] In addition, if there are descriptions such as "first", "second", etc. involved in the embodiments of the present utility model, the descriptions of "first", "second", etc. are only for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include at least one of such features. In addition, if "and / or" or "and / or" appears throughout the text, its meaning includes three parallel solutions. Taking "A and / or B" as an example, it includes Solution A, Solution B, or a solution where A and B are satisfied simultaneously. In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on the fact that those of ordinary skill in the art can implement them. When the combination of technical solutions results in contradictions or cannot be implemented, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection required by the present utility model.

[0041] It is understandable that a cement-based energy storage device is an electrochemical energy storage system that uses cement materials as the electrolyte matrix. Such an energy storage device generally has the following basic components: Cathode: The cathode is the electrode where the reduction reaction occurs in the energy storage device. During the charging process, the cathode absorbs electrons; during the discharging process, the cathode releases electrons. Anode: The anode is the electrode where the oxidation reaction occurs in the energy storage device. During the charging process, the anode releases electrons; during the discharging process, the anode absorbs electrons. Positive current collector: The positive current collector is connected to the cathode, and its function is to transfer the current from the external circuit to the cathode and back from the cathode to the external circuit. Negative current collector: The negative current collector is connected to the anode, and its function is similar to that of the positive current collector, but in the opposite direction.

[0042] Cement-based electrolyte matrix: This is the core part of the energy storage device, which is located between the cathode and the anode. The cement-based electrolyte matrix not only physically isolates the cathode and the anode, preventing them from directly contacting and causing a short circuit, but also provides a channel for ion transport, allowing ions to move between the electrodes during the charging and discharging processes. The working principle of the cement-based energy storage device is similar to that of a traditional battery, storing and releasing energy through the movement of ions between the electrodes. The advantages of such an energy storage device may include cost-effectiveness, environmental friendliness, and the use of traditional building materials (such as cement) to manufacture the electrolyte matrix.

[0043] Cement-based electrochemical energy storage technology uses solid cement-based materials as the electrolyte of the battery. The basic idea of developing the cement-based energy storage technology in this application includes adding materials that improve its electrical conductivity, such as short carbon fibers, carbon nanotubes, etc., to transform the ordinary cement-based material with low electrical conductivity into an electrolyte material with good electrical conductivity, thereby improving the energy conversion efficiency. As an important building material, cement-based materials are characterized by a large volume and wide distribution. Making them into energy storage devices can, on the one hand, reduce the building electricity cost, and on the other hand, when combined with urban community power resources, the cement-based energy storage technology can become an important supplement to grid facilities.

[0044] Making a cement - based material into an energy storage device can provide emergency power in the event of a power outage during extreme weather, such as meeting the lighting and communication needs, and enhancing the disaster tolerance of buildings in the event of a power outage caused by a disaster. On the other hand, the future development direction of buildings will inevitably be intelligent, endowing buildings with the ability of self - perception and self - regulation. If the cement - based material can provide electrical energy, it means that more sensors can be buried inside the concrete to solve their power supply problems. For example, a cement - based battery powers the structural health monitoring sensors inside the concrete. The cement - based battery can also be combined with renewable energy sources such as solar panels to provide power for monitoring systems, LED lights, network connections, etc. inside and outside the building, enhancing the intelligence and practicality of the building. The cement - based battery can provide cathodic protection for concrete infrastructure, prevent corrosion and cracks from occurring, extend the service life of buildings, and reduce maintenance costs. Making a battery from concrete uses existing materials and infrastructure, and can basically achieve zero pollution, avoiding the problems of resource consumption and environmental pollution commonly existing in traditional batteries.

[0045] Cement - based batteries are currently still in the research stage, and some technical problems such as improving energy density, reducing costs, enhancing safety, and extending lifespan need to be solved.

[0046] This application provides a cement - based energy storage device. As Figure 1 shown, the cement - based energy storage device includes a cathode plate, an anode plate, and a cement - based electrolyte matrix 1. The cathode plate is connected to the positive current collector 2, the anode plate is connected to the negative current collector 2, and a cement - based electrolyte matrix 1 is provided between the cathode plate and the anode plate. The distance between the positive current collector and the negative current collector is 1 cm to 3 cm.

[0047] It can be understood that the distance between the positive current collector and the negative current collector. Generally, it is considered that the electrode spacing will affect the current density and current efficiency of the battery. Generally speaking, the smaller the electrode spacing, the higher the current density, the higher the current efficiency, and the better the performance of the battery. However, the electrode spacing cannot be too small, otherwise it will increase the internal resistance of the battery, resulting in a voltage drop, and even electrode breakdown, causing damage or safety hazards to the battery. Therefore, the selection of the electrode spacing needs to balance the performance and safety of the battery. In this application, the distance between the positive current collector and the negative current collector is 1 cm to 3 cm, and under this range, the cement - based energy storage device has better current density and current efficiency.

[0048] In one embodiment, the size of the positive current collector and the negative current collector is 60 mm×30 mm×0.5 mm. When designing and manufacturing a battery, it is necessary to comprehensively consider the size, material, and characteristics of other battery components to achieve the best electrochemical performance and safety. In this application, when the size of the positive current collector and the negative current collector is 60 mm×30 mm×0.5 mm, it has better performance.

[0049] In one embodiment, the distance between the anode electrode sheet and the cathode electrode sheet is 10 mm. In the present application, when the distance between the anode electrode sheet and the cathode electrode sheet is 10 mm, it has good performance.

[0050] In one embodiment, the size of the cement-based energy storage device is 50 mm × 50 mm × 78 mm.

[0051] In one embodiment, at least one of the following conditions is satisfied: the active material layer of the cathode electrode sheet includes MnO2, and the anode electrode sheet includes a zinc sheet; the cathode electrode sheet includes a copper sheet, and the anode electrode sheet includes a magnesium sheet.

[0052] In one embodiment, at least one of the following conditions is satisfied: the negative current collector includes any one of a zinc sheet, AZ31 magnesium alloy, AZ91 magnesium alloy, 80-mesh AZ91 magnesium alloy mesh, aluminum sheet, aluminum mesh, iron sheet, and iron mesh; the positive current collector includes any one of carbon fiber, copper sheet, nickel mesh, nickel sheet, and nickel foam.

[0053] In one embodiment, the carbon fiber includes polyacrylonitrile-based carbon fiber or polyacrylonitrile-based carbon fiber with a 10-mm mesh.

[0054] In one embodiment, the active material layer of the cathode electrode sheet includes MnO2, and the size of the active material layer is 25 mm × 50 mm × 78 mm.

[0055] In one embodiment, the positive current collector includes carbon fiber, and the treatment steps of the carbon fiber include: preparing a three-electrode system, wherein the carbon fiber serves as the working electrode, the platinum electrode serves as the counter electrode, and the Hg / HgO electrode serves as the reference electrode; placing the three-electrode system in a first electrolyte for cyclic voltammetry treatment, and after the treatment is completed, placing the three-electrode system in a second electrolyte for cyclic voltammetry treatment until the measured current curve and voltage curve are stable; alternatively, the positive current collector includes a copper sheet, and the treatment steps of the copper sheet include: soaking the copper sheet in an acidic solution.

[0056] In one embodiment, at least one of the following conditions is satisfied: the first electrolyte and the second electrolyte include a KOH solution; the acidic solution includes a nitric acid solution.

[0057] In one embodiment, the first electrolyte and the second electrolyte for treating the carbon fiber include a KOH solution. In one embodiment, the acidic solution for treating the copper sheet includes a nitric acid solution.

[0058] In one embodiment, at least one of the following conditions is satisfied: the concentration of the first electrolyte is 4 mol / L, the concentration of the second electrolyte is 2 mol / L; the concentration of the nitric acid solution is 68%.

[0059] In one embodiment, the concentration of the first electrolyte is 4 mol / L, and the concentration of the second electrolyte is 2 mol / L.

[0060] In one embodiment, the concentration of the nitric acid solution is 68%.

[0061] In one embodiment, in the preparation of a three - electrode system, where a carbon fiber serves as the working electrode, a platinum electrode serves as the counter electrode, and a Hg / HgO electrode serves as the reference electrode; placing the three - electrode system in the first electrolyte for cyclic voltammetry treatment, and after the treatment is completed, placing the three - electrode system in the second electrolyte for cyclic voltammetry treatment until the measured current curve and voltage curve are stable. The steps include: cleaning the carbon fiber; setting up the three - electrode system, where a carbon fiber serves as the working electrode, a platinum electrode serves as the counter electrode, and a Hg / HgO electrode serves as the reference electrode; placing the three - electrode system in the first electrolyte for cyclic voltammetry treatment, with an OpenCircuit pretreatment time of 1000 s and a voltage of 100 mV / s in the cyclic voltammetry. After the treatment is completed, placing the three - electrode system in the second electrolyte for cyclic voltammetry treatment, with an OpenCircuit pretreatment time of 1000 s and a voltage of 100 mV / s in the cyclic voltammetry, until the measured current curve and voltage curve are stable.

[0062] That is, in the process of treating the carbon fiber, it includes cleaning the carbon fiber, setting up the three - electrode system, where a carbon fiber serves as the working electrode, a platinum electrode serves as the counter electrode, and a Hg / HgO electrode serves as the reference electrode; placing the three - electrode system in the first electrolyte for cyclic voltammetry treatment, with an OpenCircuit pretreatment time of 1000 s and a voltage of 100 mV / s in the cyclic voltammetry. After the treatment is completed, placing the three - electrode system in the second electrolyte for cyclic voltammetry treatment, with an OpenCircuit pretreatment time of 1000 s and a voltage of 100 mV / s in the cyclic voltammetry, until the measured current curve and voltage curve are stable.

[0063] In one embodiment, at least one of the following conditions is satisfied: the mass ratio of silicate to water - soluble salt is 1:0.4; the mass percentage of the water - soluble salt is 5%; the water - soluble salt includes potassium hydroxide and / or sodium hydroxide; the active material layer of the cathode electrode includes silicate, water - soluble salt, and MnO2, and the anode electrode includes a zinc sheet; the cathode electrode includes a copper sheet and the anode electrode includes a magnesium sheet; the negative current collector includes any one of a zinc sheet, AZ31 magnesium alloy, AZ91 magnesium alloy, 80 - mesh AZ91 magnesium alloy mesh, aluminum sheet, aluminum mesh, iron sheet, and iron mesh; the carbon fiber includes polyacrylonitrile - based carbon fiber.

[0064] In one embodiment, the active material layer of the cathode current collector includes silicate, water-soluble salt, and MnO₂. The mass ratio of silicate to water-soluble salt is 1:0.4, and corresponding mass of MnO₂ is added to the active material layer of corresponding size. The corresponding size is 25 mm × 50 mm × 78 mm, and the corresponding mass is 5 g to 15 g.

[0065] That is to say, the active material layer of the cathode current collector includes silicate, water-soluble salt, and MnO₂, wherein the mass ratio of silicate to water-soluble salt is 1:0.4, and corresponding mass of MnO₂ is added to the active material layer of corresponding size. When the size of the active material layer is 25 mm × 50 mm × 78 mm, the added mass of MnO₂ is 5 g to 15 g.

[0066] The present application also provides a power supply system, which is composed of a plurality of cement-based energy storage devices connected in series and / or in parallel.

[0067] It can be understood that the organizational form of the battery structure refers to the internal structure of the battery and the collaborative working connection method between batteries, which has a great impact on the performance of the battery. On the one hand, it will affect the energy density of the battery because a reasonable organizational form can improve the utilization rate of the active materials inside the battery. On the other hand, it affects the battery life by influencing the battery aging mechanism.

[0068] A plurality of cement-based energy storage devices can be combined in series and / or in parallel to form a power supply system for collaborative work. Connecting in series can increase the external circuit voltage, connecting in parallel can increase the external circuit current, or it can be considered that connecting in parallel can increase the battery life without changing the original battery system voltage. By combining different numbers and types of batteries, the power consumption requirements of specific voltages and higher powers can be met.

[0069] The present application also provides an energy storage building, which includes the cement-based energy storage device as described above.

[0070] It is understandable that carbon fiber, as a current collector component of an aluminum battery, has good performance, and on this basis, the carbon fiber material is further optimized. Carbon fiber is an inert material. Although it has a high electronic conductivity, its surface is flat and smooth, with very few active sites, which is not conducive to the progress of electrode reactions in battery applications. Therefore, activation treatment is required to increase the active sites on the surface of carbon fiber and improve its electrochemical activity. The activation treatment of carbon fiber can increase the hydrophilicity, porosity, specific surface area, edge sites, functional groups, etc. on the surface of the carbon fiber material without reducing the electronic conductivity, thereby improving the efficiency of processes such as its contact with the electrolyte, charge transfer, ion adsorption, and electrode reactions. In some embodiments, as a current collector material of the battery, carbon fiber needs to undergo an oxidation reaction with anions in the electrolyte to release electrons. Therefore, the introduction of oxygen atoms on the surface of carbon fiber can first improve the hydrophilicity of the fiber surface, which is beneficial to electron transfer between interfaces. Secondly, the oxygen atoms on the surface of carbon fiber can also serve as active sites to participate in electrode reactions, effectively improving the utilization rate of the electrode.

[0071] In one embodiment, the specific treatment steps for the activation of carbon fiber are as follows:

[0072] Step 1: Weigh 11.2 g and 22.4 g of analytical pure KOH and 100 mL of deionized water respectively to prepare 2 mol / L and 4 mol / L KOH solutions. Put the weighed analytical pure KOH into a large beaker, add a small amount of deionized water, and stir it with a glass rod until it is completely dissolved. The solution obtained at this time is the KOH solution to be used in the electrochemical treatment. Step 2: Cut a carbon fiber mesh with a size of 60 mm × 30 mm × 0.5 mm as the object to be treated. First, thoroughly rinse the surface of the carbon fiber mesh with deionized water until there are no obvious impurities on the surface, and then wash the surface of the carbon fiber mesh with anhydrous ethanol. After the treatment, dry it for later use. Step 3: Set up the three-electrode system required for cyclic voltammetry. Connect the working electrode to the carbon fiber mesh, use a platinum electrode as the counter electrode of the three-electrode system, use a Hg / HgO electrode as the reference electrode, and use the prepared 4 mol / L potassium hydroxide solution as the solution. Treat the carbon fiber mesh according to a certain time and voltage. Step 4: Place the carbon fiber mesh after electrochemical treatment under flowing deionized water for thorough cleaning, and dry it for later use. Step 5: Put the dried carbon fiber mesh into a 2 mol / L KOH solution and perform cyclic voltammetry (CV) treatment on it using the three-electrode system. The Open Circuit pretreatment time in cyclic voltammetry is controlled at 1000 s, and the voltage is controlled at 100 mV / s. Then, use a current of 100 mV / s to perform cyclic current treatment on it until the measured current-voltage curve is stable. Step 6: Take out the carbon fiber mesh from the solution and dry it for later use.

[0073] In one embodiment, the processing step of the copper sheet is to directly place the copper sheet into a 68% nitric acid solution for 20 s, then rinse it with clean water and absolute ethanol, and dry it to obtain a copper current collector with a corroded surface.

[0074] In one embodiment, the sizes of the positive current collector and the negative current collector are uniformly controlled at 60 mm × 30 mm × 0.5 mm. Connect the assembled battery to a 10 Ω resistor, and use an ammeter and a voltmeter with real-time data acquisition function to measure the current and voltage of the resistor.

[0075] Example

[0076] Example 1

[0077] Preparation of the cement-based electrolyte matrix: Add KOH solution to the sodium silicate material, and perform curing and solidification in sequence to obtain the cement-based electrolyte matrix. The mass ratio of sodium silicate to KOH solution is 1:0.4, and the mass concentration of the KOH solution is 5%.

[0078] Preparation of the cathode plate: Add KOH solution and MnO2 powder to the sodium silicate material, and perform curing and solidification in sequence to obtain the cathode plate matrix. Among them, 5 g of MnO2 powder is added to the cathode plate matrix of 25 mm × 50 mm × 78 mm.

[0079] Among them, before solidification, insert an anode plate (high-purity zinc sheet with a purity greater than 99.99%) and a negative current collector (zinc sheet) into the cement-based electrolyte matrix with a size of 25 mm × 50 mm × 78 mm. The negative current collector is exposed outside the cement-based electrolyte matrix. Insert a positive current collector (copper sheet) into the cathode plate matrix with a size of 25 mm × 50 mm × 78 mm, and the positive current collector is exposed outside the cathode plate matrix.

[0080] The distance between the zinc sheet and the copper sheet is 1 cm. Set a 10 Ω resistor as the external circuit load in the discharge experiment. After the battery is made, let it stand still. When the cement-based material finally sets, measure the open-circuit voltage of the battery. After the cement-based material finally sets, connect a 10 Ω resistor load to the external circuit, discharge the battery continuously, and measure the external circuit voltage and current values.

[0081] Example 2

[0082] The method of this example is the same as that of Example 1, except that the addition amount of MnO2 powder is 10 g.

[0083] Example 3

[0084] The method of this example is the same as that of Example 1, except that the addition amount of MnO2 powder is 15 g.

[0085] Measuring the current and voltage of the external circuit of a battery can provide information about the current state of the battery. By observing the changes in current and voltage, the charging level, discharge state, and overall performance of the battery can be judged. There is a relationship between the current and voltage of the battery and its capacity. By measuring the current and voltage of the battery under a specific load, the capacity of the battery, that is, the electrical energy that the battery can provide, can be estimated. Long-term monitoring of current and voltage can be used to predict the battery life. The discharge external circuit voltage diagrams of batteries with different addition amounts of MnO2 powder are as Figure 3 shown. The external circuit voltages of the batteries with 5 g, 10 g, and 20 g of MnO2 powder added mainly concentrate in the regions of 0.035 mV, 0.095 mV, and 0.105 mV respectively.

[0086] Example 4

[0087] The method of this example is similar to that of Example 1, except that no MnO2 powder is added, the cathode plate is a copper sheet, the positive current collector is a copper sheet, and the negative current collector is an AZ31 magnesium alloy. The anode plate is a magnesium sheet with dimensions of 60 mm × 30 mm × 0.5 mm, and the internal active material of the metal is fully exposed using sandpaper. A copper sheet is selected as the current collector unit in the experiment. The magnesium sheet of the anode plate and the copper sheet of the cathode plate are inserted into the mixed cement-based electrolyte matrix at an interval of 10 mm.

[0088] Example 5

[0089] The method of this example is the same as that of Example 4, except that the negative current collector is an AZ91 magnesium alloy.

[0090] Example 6

[0091] The method of this example is the same as that of Example 4, except that the negative current collector is an 80-mesh AZ91 magnesium alloy mesh.

[0092] The discharge external circuit voltage-time diagram of the magnesium alloy battery is as Figure 4 shown. The peak voltage and the voltage level under the same discharge time using an AZ91 magnesium alloy sheet are both higher than those using an AZ31 magnesium alloy sheet as the electrode material. However, after 60 minutes of discharge, the final voltage levels of both tend to the same level, that is, below 0.6 mV. Using an 80-mesh AZ91 magnesium alloy mesh as the electrode material, the peak voltage is always higher than that of the battery using an AZ91 alloy sheet as the electrode during the discharge period. Because the mesh metal electrode has a larger specific surface area, while the surface of the sheet magnesium alloy material is smoother and not easy to adsorb charges, using the mesh metal material as the electrode makes the peak voltage and discharge life higher.

[0093] Example 7

[0094] The method of this example is similar to that of Example 4, except that the negative current collector is an aluminum sheet and a copper sheet is used as the positive current collector.

[0095] Example 8

[0096] The method of this example is the same as that of Example 7, except that a polyacrylonitrile-based carbon fiber with a 10 mm mesh is used as the positive current collector.

[0097] Example 9

[0098] The method of this example is the same as that of Example 7, except that the negative current collector is an aluminum mesh.

[0099] The voltage-time graph of the discharge external circuit of the aluminum electrode battery is as Figure 4 shown. The external circuit voltage of the battery is mainly concentrated in the range of 1.2 V to 1.4 V. The current-voltage peak value and the voltage value within the same discharge time of the Al mesh-Cu sheet battery, Al sheet-C mesh, and Al sheet-Cu sheet batteries decrease in turn. This shows that the Al mesh has stronger electrochemical reaction performance than the Al sheet, and the carbon fiber mesh is more compatible with the electrolyte material than the copper sheet.

[0100] Example 10

[0101] The method of this example is the same as that of Example 7, except that the positive current collector is subjected to an activation treatment. Method for activating the copper sheet: directly place the copper sheet in a 68% nitric acid solution for 20 s, then rinse it with water and anhydrous ethanol, and dry it to obtain a copper current collector with a corroded surface.

[0102] Example 11

[0103] The method of this example is the same as that of Example 8, except that the carbon fiber mesh of the positive current collector is subjected to an activation treatment.

[0104] Carbon fiber has good performance as a current collector component of an aluminum battery. On this basis, the carbon fiber material is further optimized. The specific treatment steps are as follows:

[0105] The relative molecular mass of KOH is 56. Therefore, 11.2 g and 22.4 g of analytical pure KOH, and 100 mL of deionized water were weighed separately here to prepare 2 mol / L and 4 mol / L KOH solutions. The weighed analytical pure KOH was placed in a large beaker, and a small amount of deionized water was added. Stir it with a glass rod to completely dissolve it. The solution obtained at this time is the KOH solution to be used in the electrochemical treatment. Cut a carbon fiber mesh with a size of 60 mm × 30 mm × 0.5 mm as the object to be treated. First, thoroughly rinse the surface of the carbon fiber mesh with deionized water until there are no obvious impurities on the surface, and then clean the surface of the carbon fiber mesh with anhydrous ethanol. After treatment, dry it for later use. Set up the three-electrode system required for cyclic voltammetry. The working electrode is connected to the carbon fiber mesh, a platinum electrode is used as the counter electrode of the three-electrode system, and a Hg / HgO electrode is used as the reference electrode. The solution used is the prepared 4 mol / L potassium hydroxide solution. Treat the carbon fiber mesh according to a certain time and voltage. Thoroughly wash the electrochemically treated carbon fiber mesh under flowing deionized water and dry it for later use. Put the dried carbon fiber mesh into the 2 mol / L KOH solution and perform cyclic voltammetry treatment on it using the three-electrode system. The Open Circuit pretreatment time in cyclic voltammetry is controlled at 1000 s, and the voltage is controlled at 100 mV / s. Then, similarly use a current of 100 mV / s to perform cyclic current treatment on it until the measured current-voltage curve is stable. Take out the carbon fiber mesh from the solution and dry it for later use.

[0106] The battery discharge voltage-time graph of the copper sheet and the carbon fiber after treatment is as Figure 5 shown. For the battery made of the copper sheet and the carbon fiber after treatment, the voltage is significantly higher than that of the untreated material. The surface of the material treated by electrochemistry and chemical agents will change from smooth to rough, and the more rough surface will have better compatibility with the cement-based solid electrolyte. At the same time, the rough surface exposes more active sites, which is beneficial for the current collector to collect charges and can also provide charge exchange sites for the active material. The current collector element after surface treatment can enhance the battery performance.

[0107] Example 12

[0108] The method of this example is similar to that of Example 4, except that the positive current collector uses a nickel sheet and the negative current collector uses an iron sheet.

[0109] Example 13

[0110] The method of this example is the same as that of Example 12, except that the positive current collector uses a nickel mesh.

[0111] Example 14

[0112] The method of this example is the same as that of Example 12, except that the negative current collector uses an iron mesh.

[0113] Example 15

[0114] The method of this example is the same as that of Example 14, except that the positive current collector is made of nickel foam.

[0115] The open-circuit voltage during charge and discharge of the nickel-iron rechargeable cement-based energy storage device is as Figures 5 to 9 shown. Among the positive electrode materials of the battery, nickel foam is superior to nickel mesh, and both of them are superior to nickel sheet; among the negative current collector materials of the battery, iron mesh is superior to iron sheet. This also shows that the electrode current collector material with a larger specific surface area can improve the battery performance.

[0116] Example 16

[0117] The method of this example is the same as that of Example 7, except that different current collector spacings of 1 cm, 2 cm, and 3 cm are used in this example.

[0118] The peak voltages at electrode spacings of 1 cm, 2 cm, and 3 cm are 95.36 mV, 72.38 mV, and 57.53 mV respectively, and the peak currents are 95.36 mA, 72.38 mA, and 57.53 mA respectively. It can be seen that the peak voltage and peak current decrease with the increase of the electrode spacing. The electrode spacing refers to the distance between the positive and negative electrodes of the battery. Generally, it is considered that the electrode spacing will affect the current density and current efficiency of the battery. Generally speaking, the smaller the electrode spacing, the higher the current density, the higher the current efficiency, and the better the battery performance. However, the electrode spacing cannot be too small, otherwise it will increase the internal resistance of the battery, resulting in a voltage drop, and even electrode breakdown, causing damage or safety hazards to the battery. Therefore, the selection of the electrode spacing needs to balance the performance and safety of the battery.

[0119] Example 17

[0120] The method of this example adopts the same battery scheme as that of Example 7. Two cement-based energy storage devices are connected in series and two cement-based energy storage devices are connected in parallel respectively.

[0121] The total voltage of the parallel-connected batteries is the same as that of a single battery, and since the total capacity of the parallel circuit increases, the circuit can provide a larger current without reducing the voltage. Compared with a single cement-based energy storage device, connecting the batteries in parallel increases the voltage across the load resistance. Connecting the batteries in parallel can improve the overall discharge performance of the power supply system. Connecting the batteries in series and parallel can make multiple batteries work together as a power supply system. Connecting in series can increase the external circuit voltage, and connecting in parallel can increase the external circuit current, or it can be considered that connecting in parallel can increase the battery life without changing the original battery system voltage. By combining different numbers and types of batteries, the power consumption requirements of specific voltages and higher powers can be met.

[0122] The above are only exemplary embodiments of the present utility model, and do not limit the patent scope of the present utility model accordingly. Any equivalent structural transformation made under the technical concept of the present utility model by using the content of the specification and drawings of the present utility model, or any direct / indirect application in other related technical fields, is included in the patent protection scope of the present utility model.

Claims

1. A cement-based energy storage device, characterized in that: include: A cathode electrode sheet connected to the positive electrode current collector; An anode electrode sheet connected to a negative electrode current collector; and a cement-based electrolyte matrix, wherein the cement-based electrolyte matrix is ​​disposed between the cathode electrode sheet and the anode electrode sheet, and the distance between the positive electrode current collector and the negative electrode current collector is 1 cm to 3 cm.

2. The cement-based energy storage device according to claim 1, characterized in that: The dimensions of the positive electrode current collector and the negative electrode current collector are 60 mm×30 mm×0.5 mm.

3. The cement-based energy storage device according to claim 1, characterized in that: The distance between the anode electrode piece and the cathode electrode piece is 10 mm.

4. The cement-based energy storage device according to claim 1, characterized in that: The size of the cement-based energy storage device is 50 mm×50 mm×78 mm.

5. The cement-based energy storage device according to any one of claims 1 to 4, characterized in that: Meet at least one of the following conditions: The active material layer of the cathode electrode sheet includes MnO2, and the anode electrode sheet includes a zinc sheet; The cathode electrode plate includes a copper plate, and the anode electrode plate includes a magnesium plate.

6. The cement-based energy storage device according to any one of claims 1 to 4, characterized in that: Meet at least one of the following conditions: The negative electrode current collector comprises any one of a zinc sheet, an AZ31 magnesium alloy, an AZ91 magnesium alloy, an 80-mesh AZ91 magnesium alloy mesh, an aluminum sheet, an aluminum mesh, an iron sheet, and an iron mesh; The positive electrode current collector includes any one of carbon fiber, copper sheet, nickel mesh, nickel sheet, and nickel foam.

7. The cement-based energy storage device according to claim 6, characterized in that: The carbon fiber includes polyacrylonitrile-based carbon fiber or polyacrylonitrile-based carbon fiber with a mesh size of 10 mm.

8. The cement-based energy storage device according to claim 5, characterized in that: The active material layer of the cathode electrode sheet includes MnO2, and the size of the active material layer is 25 mm×50 mm×78 mm.

9. A power supply system, characterized in that: The power supply system comprises a plurality of cement-based energy storage devices connected in series and / or in parallel, and the cement-based energy storage device comprises the cement-based energy storage device as described in any one of claims 1 to 8.

10. An energy storage building, characterized in that: The energy storage building comprises the cement-based energy storage device according to any one of claims 1 to 8.

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