Energy storage battery and preparation method thereof

Abstract

The application belongs to the field of energy storage batteries, and discloses an energy storage battery and a preparation method thereof. The energy storage battery comprises a positive electrode sheet, a negative electrode sheet and a solid electrolyte. The solid electrolyte comprises wind sand, cement, inorganic insulating fiber, sodium salt and a specific type of additive. The energy storage battery first proposes to use wind sand as the raw material of the solid electrolyte of the battery, and cooperates with the inorganic insulating fiber, the sodium salt and the specific type of additive to obtain a cement-based energy storage battery with high safety, high electronic insulation and high ion transmission capacity, and good cycle stability, expands the application scene of the wind sand material, realizes the resource utilization of the wind sand, can delay the harm caused by desertification and produce huge economic benefits, and the battery can be directly made into building components to realize the integration of "energy storage building materials".

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of energy storage batteries, and relates to an energy storage battery and a preparation method thereof. The energy storage battery uses a cement-based solid electrolyte, has the advantages of low cost and high safety, and has a high application prospect in the field of energy storage. BACKGROUND

[0002] An electrochemical energy storage system is a key system for realizing the conversion, storage and control of renewable clean energy, and is used to realize the conversion between chemical energy and electrical energy, and is required to have the characteristics of safety, low cost, high efficiency and long service life. With the development of new energy, the demand for energy storage products is increasingly urgent. A cement-based battery uses a cement-based material as a structural electrolyte and has a charging and discharging capacity, and is a promising structural energy storage integrated composite material, and is considered to be one of the solutions for large-scale energy storage in the future, and 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 of buildings in the case of power interruption in disasters. At present, research on cement-based energy storage devices has been started. CN119029326A discloses a cement-based energy storage device, which includes a cathode sheet, an anode sheet and a cement-based electrolyte matrix, the cathode sheet is connected with a positive current collector, the anode sheet is connected with a negative current collector, and the cement-based electrolyte matrix is arranged between the cathode sheet and the anode sheet, and the raw materials of the cement-based electrolyte matrix include silicate and water-soluble salt. CN118040066A discloses a cement-based lithium battery, which combines the functional materials commonly used in lithium batteries, including lithium cobaltate, lithium iron phosphate and polyethylene oxide, with cement materials, uses iron powder to prepare the electrolyte of the battery, and uses polyvinylidene fluoride and butadiene rubber to prepare the adhesive layer of the battery, thereby forming a new type of cement-based lithium battery that can be charged and discharged multiple times. The battery has high energy density, long service life and high compressive strength retention rate, and can be better used in the field of construction engineering, and has a good application prospect. However, the research on cement-based batteries is still in its infancy, and there are many problems, and the performance still has a lot of room for improvement.

[0003] Wind-blown sand refers to the sand formed by the accumulation of a large amount of rock debris carried by the wind in desert areas. It is often found in deserts and gobi areas in China. The particles are uniform, with a particle size of 0.075-0.5mm, a small fineness modulus, and a relatively concentrated particle size distribution. Wind-blown sand is different from common building materials such as river sand or sea sand. Its particle size range is narrower, its density is higher, its porosity is lower, and its water retention capacity is poor. Therefore, river sand or sea sand cannot be directly replaced by wind-blown sand. Wind-blown sand is widely distributed in deserts and has abundant reserves. Desertification is one of the most serious problems facing us. Desertification area in China has reached 27% of the total land area and is still expanding. If wind-blown sand can be effectively utilized, it can be turned into treasure and to some extent reduce the deterioration of the ecological environment. Domestic application research of wind-blown sand is mainly used for roadbed and foundation. Although this method can solve the problem of shortage of river sand and sea sand to some extent, it cannot realize high-value utilization of wind-blown sand. Some studies have shown that sand can be used as a filler in energy storage batteries. For example, CN115863866A discloses a structure energy storage integrated concrete matrix battery. The concrete matrix is formed by foamed concrete, which is mixed with short fibers. The concrete matrix has an internal pore structure. The battery electrode includes a current collector, a tab, and the concrete matrix. The surface of the current collector is provided with an electrode active material, a conductive agent, and a binder. The concrete matrix provides a space for the current collector. The internal pore structure of the concrete matrix contains alkaline electrolyte, which is sealed by a surface cover layer. The battery maintains its energy storage performance while providing excellent mechanical properties through the concrete matrix. CN116053612A discloses a cement-based battery and a preparation method thereof. The cement-based battery includes a conductive cement base and a plurality of battery bodies connected in series in the conductive cement base. The conductive cement base is formed by pouring a cement-based electrolyte material. The cement-based electrolyte material includes the following components by weight percentage: cement 14.9%-65.0%, conductive material 0.1%-2.8%, fine aggregate 0-71.7%, water reducing agent 0-0.53%, and water 21.1-40%. The flowability of the cement-based electrolyte material is greater than or equal to 160mm. The cement-based battery includes a plurality of series-connected battery bodies, which improves the overall energy storage capacity and provides stable current for a long time without external power supply.CN118800978A discloses a rechargeable cement-based battery, which comprises an anode, an electrolyte and a cathode, the electrolyte is provided with an anode and a cathode at both ends, the anode is a galvanized metal iron carbon fiber mesh, the cathode is a galvanized metal nickel carbon fiber mesh, and the electrolyte is a cement-based material; the cement-based material comprises the following components by weight percentage: cement 14.9%-65.0%, conductive material 0.1%-2.8%, fine aggregate 0-71.7%, water reducing agent 0-0.53% and water 21.1-40%; the positive and negative poles of the battery body are formed by electroplating iron and nickel on the carbon fiber mesh, which improves the charging and discharging efficiency of the battery. CN117577964A discloses a rechargeable cement-based battery, which comprises a cement-based electrolyte and metal positive and negative electrodes inserted in the cement-based electrolyte, and part of the metal positive and negative electrodes are exposed to the cement-based electrolyte; or the battery comprises a cement-based positive electrode, a cement-based electrolyte and a cement-based negative electrode which are stacked in sequence; wherein the raw materials of the cement-based electrolyte include Portland cement, water, water-soluble salt and quartz sand. It uses cheap and abundant cement materials to prepare rechargeable cement-based batteries, which has low cost and excellent electrical performance, and can lay the foundation for building structure energy storage, and can be used as an alternative solution to energy crisis. The current cement battery mostly uses the internal porous structure formed by cement solidification to fill electrolyte or add conductive salt gel electrolyte, and this structure needs excellent sealing property during battery charging and discharging to avoid the loss of electrolyte volatilization, which is not conducive to the long-term use of the battery. Although the aeolian sand resources are abundant in the desert, the particle size is too small, the particle size is mostly less than 0.25mm, the gradation is poor and the particle is smooth, the plasticity is poor, which cannot be simply replaced by conventional fillers for energy storage battery, in addition, the solid electrolyte cement energy storage battery also has low ion conductivity, when the carbon material is introduced, the ion conductivity can be improved, but the electronic conductivity is also increased, which may cause local short circuit and certain safety hazard. At present, there is no record of aeolian sand used in energy storage battery, if the aeolian sand can be applied to energy storage battery, not only the harm of desertification can be delayed, but also great economic benefits can be obtained, therefore, relevant technical solutions are needed to fill the research blank of aeolian sand in the field of energy storage. SUMMARY

[0004] In order to solve the defects in the prior art, the present application provides a kind of energy storage battery and preparation method thereof, which comprises positive pole piece, negative pole piece and the solid electrolyte that separates positive pole piece, negative pole piece, the solid electrolyte comprises aeolian sand, cement, inorganic insulating fiber, sodium salt and the selected Na3Zr2Si2PO 12 , Na3Zr2Si3P3O 14 , Li7La3Zr2O 12 , Li 6.4 La3Zr 1.4Ta 0.6 O 12 , NaFePO4, Na3PS4, Na3PSe4, Na 10 SnP2S 12 , Na 1.4 Al 0.4 Ti 1.6 (PO4)3 and Na 0.5 Bi 0.5 TiO3. The energy storage battery provides a new cement-based energy storage battery scheme, the electrolyte mainly uses wind sand and cement as the base material, can significantly reduce the electrolyte cost, and does not need rare metals, has obvious cost advantage and resource availability; meanwhile, the battery has high safety, the full solid inorganic system cement-based electrolyte does not contain flammable organic solvents, completely eliminates the risk of burning and explosion, and the zinc or iron metal negative electrode and the rigid electrolyte synergistically act, effectively inhibits dendrite penetration, has good electronic insulation and ion transmission capacity, has good specific capacity and cycle stability. In addition, the battery has high mechanical strength and good stability, can effectively prevent internal short circuit or structural damage of the battery, the battery module has high compressive strength, can be directly used as a building component (such as a wall body and a foundation), and realizes the integrated use of "energy storage building materials".

[0005] To achieve the above-mentioned purposes of the present application, the present application provides an energy storage battery, comprising a positive electrode sheet, a negative electrode sheet and a solid-state electrolyte separating the positive electrode sheet and the negative electrode sheet, the solid-state electrolyte comprising: wind sand, cement, inorganic insulating fiber, sodium salt and additive, the additive being selected from at least one of Na3Zr2Si2PO 12 , Na3Zr2Si3P3O 14 , Li7La3Zr2O 12 , Li 6.4 La3Zr 1.4 Ta 0.6 O 12 , NaFePO4, Na3PS4, Na3PSe4, Na 10 SnP2S 12 , Na 1.4 Al 0.4 Ti 1.6 (PO4)3 and Na 0.5 Bi 0.5 TiO3. The use of sodium salt and specific additive can provide effective sodium ion transmission channel and optimize electrolyte ion transmission performance, enhance the ion conductivity of the electrolyte, and improve the charge and discharge efficiency and capacity retention rate of the battery.

[0006] Further, the positive electrode sheet comprises a positive electrode current collector and a positive electrode active layer attached to the positive electrode current collector, the positive electrode active layer comprises 90wt%-95wt% of activated carbon, 5wt%-10wt% of a binder selected from one of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethyl cellulose, the positive electrode active layer has a thickness of 0.5-3mm, and the positive electrode current collector is a copper foil or an aluminum foil.

[0007] Further, the negative electrode sheet is a metal plate, the metal is selected from one of iron and zinc, and the metal plate has a thickness of 1-10mm.

[0008] Further, the inorganic insulating fiber is selected from at least one of alkali-free glass fiber, alumina fiber, basalt fiber, mullite fiber and aluminum silicate fiber, and the cement is one of sulphoaluminate cement and portland cement. The introduction of the inorganic insulating fiber further enhances the toughness and crack resistance of the cement-based electrolyte substrate, and the stability is strong. Meanwhile, the introduction of the aeolian sand and the inorganic insulating fiber can also synergistically adjust the pore structure of the cement-based electrolyte substrate, providing more migration paths for ions. Meanwhile, it is accidentally found in the experiment that when the aeolian sand and the inorganic insulating fiber are used in a specific cement, the concrete obtained after normal curing treatment has a good pore structure inside, which is good for promoting the ion transmission in the electrolyte, and the internal pores do not have an adverse effect on the mechanical structure of the concrete.

[0009] Further, the mass fraction of each component in the solid-state electrolyte is 40-60wt% of aeolian sand, 20-40wt% of cement, 1-5wt% of inorganic insulating fiber, 1-10wt% of sodium salt and 5-10wt% of additive. There is no special limitation on the source of the aeolian sand and the cement. The aeolian sand in the present application is sourced from the Kubqi Desert and is directly used as a raw material after special treatment. The average particle size of the aeolian sand is 0.07-0.20mm.

[0010] Further, the preparation method of the positive electrode sheet is as follows: activated carbon and a binder are weighed according to the mass ratio of 90-95:5-10, the activated carbon and the binder are blended in an organic solvent NMP, and the positive electrode slurry is formed after high-speed stirring. Then, the positive electrode slurry is uniformly coated on the positive electrode current collector, and the positive electrode sheet is prepared after drying, rolling and slitting.

[0011] Further, the thickness of the solid-state electrolyte is 5-50mm, the sodium salt is one of sodium nitrate and sodium sulfate, and the preparation method of the solid-state electrolyte is as follows:

[0012] 1) aeolian sand, cement, inorganic insulating fiber, sodium salt and additive are weighed according to the proportion;

[0013] 2) Put the aeolian sand, cement, inorganic insulating fiber and additive into a mixing container and dry mix for 10-60 min to obtain a mixed material; dissolve the sodium salt in water to obtain a sodium salt solution with a concentration of 0.5-1 M;

[0014] 3) Put the mixed material obtained in step 2) into the sodium salt solution and stir for 60-200 min until uniformly dispersed to obtain a slurry; pour the slurry into a mold, vibrate and flatten, and then solidify and heat treat to obtain the product.

[0015] Further, the solidification specifically comprises: placing the vibrated and flattened mold in an environment with a temperature of 25 DEG C and a humidity of 50+ / -5% for 10-20 h; then placing the mold in an environment with a humidity of 90+ / -5% for 5-10 days to completely hydrate the cement; then drying at 60-80 DEG C for 2-5 days and demolding; and the heat treatment comprises: placing the demolded product in an environment with a temperature of 150-250 DEG C for 1-5 h.

[0016] The application also provides a preparation method of the energy storage battery, which comprises the following steps:

[0017] S1: preparing a positive electrode sheet: weighing active carbon and a binder according to a mass ratio of 90-95:5-10, mixing the active carbon and the binder in NMP, stirring at high speed to form a positive electrode slurry, uniformly coating the positive electrode slurry on a positive electrode current collector, and then drying, rolling, and cutting to obtain the positive electrode sheet;

[0018] S2: preparing a solid electrolyte slurry: weighing aeolian sand, cement, inorganic insulating fiber, sodium salt, and additive according to a proportion; putting the aeolian sand, cement, inorganic insulating fiber, and additive into a mixing container and dry mixing for 10-60 min to obtain a mixed material; dissolving the sodium salt in water to obtain a sodium salt solution with a concentration of 0.5-1 M; and putting the mixed material into the sodium salt solution and stirring for 60-200 min until uniformly dispersed to obtain a slurry;

[0019] S3: preparing a battery: placing a positive electrode sheet and a negative electrode sheet in front of and behind a mold respectively, with the positive electrode active layer facing the negative electrode sheet; then pouring the slurry into the mold, vibrating and flattening, adjusting the distance between the positive and negative electrode sheets, and then solidifying and heat treating to obtain the product.

[0020] Further, the additive is selected from Na3Zr2Si2PO 12 , Na3Zr2Si3P3O 14 , Li7La3Zr2O 12 , Li 6.4 La3Zr 1.4Ta 0.6 O 12 , NaFePO4, Na3PS4, Na3PSe4, Na 10 SnP2S 12 , Na 14 Al 0.4 Ti 1.6 (PO4)3 and Na 0.5 Bi 0.5 TiO3.

[0021] The binder is selected from one of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethyl cellulose, the positive active layer thickness is 0.5-3mm, the positive current collector is copper foil or aluminum foil, the negative electrode plate is a metal plate, the metal is selected from one of iron and zinc, the thickness of the metal plate is 1-10mm, the inorganic insulating fiber is selected from at least one of alkali-free glass fiber, alumina fiber, basalt fiber, mullite fiber and aluminum silicate fiber, and the cement is one of sulphoaluminate cement or Portland cement.

[0022] Further, the mass fraction of each component in the solid-state electrolyte is 40-60wt% of wind-blown sand, 20-40wt% of cement, 1-5wt% of inorganic insulating fiber, 1-10wt% of sodium salt and 5-10wt% of additives.

[0023] Further, the solidification specifically comprises: placing the vibrated and smoothed mold in an environment with a temperature of 25 DEG C and a humidity of 50+ / -5% for 10-20h; then placing the mold in an environment with a humidity of 90+ / -5% for 5-10 days to completely hydrate the cement; then drying at 60-80 DEG C for 2-5 days and demolding; and the heat treatment comprises placing the demolded product in a static state at 150-250 DEG C for 1-5h.

[0024] Compared with the prior art, the beneficial effects of the technical scheme of the present application are as follows:

[0025] 1. The present application provides a new cement-based energy storage battery scheme, which first proposes the application of wind-blown sand in energy storage batteries and first successfully prepares an energy storage battery based on wind-blown sand, expands the application scenarios of wind-blown sand, effectively improves the utilization of wind-blown sand resources, can delay the harm caused by desertification and produce huge economic benefits, and fills the research gap of wind-blown sand in the field of energy storage.

[0026] 2、The electrolyte mainly uses aeolian sand and cement as the base material, the raw material is safe and non-toxic, the aeolian sand is a kind of natural resource, is widely distributed and low in price, the cement is a common material in the building industry, the production cost is low, the inorganic insulating fiber is also cheap and easy to obtain, compared with the currently widely used battery system, the cost is low, the raw material is rich, and the cost is controllable. Meanwhile, the cement-based material can be recycled after the service life, the solid electrolyte does not use organic solvent, and the waste battery is easy to handle.

[0027] 3、The battery has high safety, does not contain flammable organic solvent, completely eliminates the risk of burning and explosion, and the zinc or iron metal negative electrode cooperates with the rigid electrolyte, effectively inhibits the penetration of dendrites, the construction of the solid electrolyte system of the application has good electronic insulation and ion transmission capacity, in a specific cement system, the use of aeolian sand and inorganic insulating fiber can produce synergistic effect, can adjust the pore structure of the cement-based electrolyte base material, provide more paths for ion transmission, and increase the ion conductivity.

[0028] 4、The battery has high mechanical strength, does not need additional support, can withstand certain external force impact, the inorganic insulating fiber further enhances the toughness and crack resistance of the material, the cement-based solid electrolyte shows good chemical and physical stability in long-term use, and is not easy to be damaged in structure or performance decay. The battery of the application has good stability, good specific capacity and cycle stability, can effectively prevent internal short circuit or structural damage of the battery, the battery module has high compressive strength, can be directly used as a building component (such as a wall, a foundation), has certain integrated application prospect of "energy storage building material", in addition, can be widely used in large-scale matching energy storage of power grid energy storage or renewable energy systems such as solar energy / wind energy. DETAILED DESCRIPTION

[0029] In order to make the technical problems solved by the application, the technical solutions adopted and the technical effects reached more clear, the technical solutions of the embodiments of the application will be further described in detail below. Obviously, the described embodiments are only part of the embodiments of the application, not all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor belong to the protection scope of the application.

[0030] It should be noted that the reference to "embodiments" in this text means that the specific features, structures or characteristics described in combination with the embodiments can be included in at least one embodiment of the application. The appearance of this phrase at various places in the specification does not necessarily mean the same embodiment, nor is it an independent or alternative embodiment to other embodiments. Those skilled in the art explicitly and implicitly understand that the embodiments described herein can be combined with other embodiments.

[0031] The experimental methods in the following examples are all conventional methods unless otherwise specified. The materials, reagents, etc. used in the following examples are all commercially available unless otherwise specified.

[0032] Example 1

[0033] An energy storage battery comprising a positive electrode sheet, a negative electrode sheet and a solid-state electrolyte, the negative electrode sheet is an iron plate with a thickness of 1 mm, and the solid-state electrolyte comprises: aeolian sand 53 wt%, sulphate cement 40 wt%, alkali-free glass fiber 1 wt%, sodium nitrate 1 wt% and Na3Zr2Si2PO 12 5 wt%,

[0034] The preparation method of the energy storage battery is as follows:

[0035] S1: Preparation of the positive electrode sheet: active carbon and polytetrafluoroethylene are weighed according to the mass ratio of 90:10, and then mixed in NMP to form a positive electrode slurry after high-speed stirring. Then the positive electrode slurry is uniformly coated on a copper foil, and after drying, rolling, and cutting, a positive electrode sheet with an active layer thickness of 0.5 mm is obtained;

[0036] S2: Preparation of the solid-state electrolyte slurry: aeolian sand, sulphate cement, alkali-free glass fiber, sodium nitrate and Na3Zr2Si2PO 12 are weighed according to the proportion, and then mixed and put into a mixing container for dry mixing. After 10 minutes of mixing, a uniformly mixed mixture is obtained. Sodium salt is dissolved in water to obtain a sodium salt solution with a concentration of 0.5 M. The mixture is added to the sodium salt solution and stirred for 60 minutes until it is uniformly dispersed to obtain a slurry; 12

[0037] S3: Preparation of the battery: the positive electrode sheet and the iron plate are placed in front of and behind the mold, respectively, with the positive active layer facing the iron plate. Then the slurry is poured into the mold and leveled by shaking, and the distance between the positive electrode sheet and the iron plate is adjusted to 5 mm. The leveled mold is then placed in an environment with a temperature of 25°C and a humidity of 50±5% for 10 hours. Then the mold is placed in an environment with a humidity of 90±5% for 5 days to allow the cement to fully hydrate. Then the mold is dried at 60°C for 2 days and demolded. The demolded product is placed in a 150°C environment for 1 hour.

[0038] The battery is tested, and the voltage of the energy storage battery is 1.85 V, the specific energy is 22.07 Wh / Kg, the ionic conductivity is 2.3 mS / cm, and the capacity retention rate after 1000 hours of storage is 83%. After standardizing the battery mass, it is calculated that the capacity of the energy storage battery is about 22 Wh.

[0039] Example 2 ​

[0040] An energy storage battery, comprising a positive electrode sheet, a negative electrode sheet and a solid-state electrolyte, the negative electrode sheet is a zinc plate with a thickness of 10 mm, and the solid-state electrolyte comprises: aeolian sand 55wt%, silicate cement 20wt%, aluminum oxide fiber 3wt%, sodium sulfate 10wt% and Na3PS4 10wt%,

[0041] The preparation method of the energy storage battery is as follows:

[0042] S1: preparing the positive electrode sheet: taking active carbon and polyvinylidene fluoride according to a mass ratio of 95:5, blending the active carbon and polyvinylidene fluoride in NMP, and forming a positive electrode slurry after high-speed stirring, then uniformly coating the positive electrode slurry on an aluminum foil, and obtaining a positive electrode sheet with an active layer thickness of 3 mm after drying, rolling, and cutting;

[0043] S2: preparing a solid-state electrolyte slurry: taking aeolian sand, silicate cement, aluminum oxide fiber, sodium sulfate and Na3PS4 according to the proportion; mixing the silicate cement, aluminum oxide fiber, sodium sulfate and Na3PS4, and then putting them into a mixing container for dry mixing for 60 min to obtain a uniformly mixed mixture; dissolving the sodium sulfate in water to obtain a sodium salt solution with a concentration of 1M; adding the mixture into the sodium salt solution, and stirring for 200 min until the slurry is uniformly dispersed;

[0044] S3: preparing the battery: placing the positive electrode sheet and the zinc plate in front of and behind the mold respectively, with the positive active layer facing the zinc plate; then pouring the slurry into the mold, leveling it by vibration, and adjusting the distance between the positive and negative electrode sheets to 50 mm; then placing the leveled mold in an environment with a temperature of 25°C and a humidity of 50±5% for 20 h; then placing the mold in an environment with a humidity of 90±5% for 10 days to completely hydrate the cement; then drying at 80°C for 5 days and demolding; and placing the demolded product in a 250°C environment for 5 h.

[0045] The battery is tested, and the voltage of the energy storage battery is 2.11V, the specific energy is 24.4Wh / Kg, the ionic conductivity is 3.5mS / cm, and the capacity retention rate after 1000h is 86%. After standardizing the battery quality, it is calculated that the capacity of the energy storage battery is about 24Wh.

[0046] Example 3

[0047] An energy storage battery, comprising a positive electrode sheet, a negative electrode sheet and a solid-state electrolyte, the negative electrode sheet is a zinc plate with a thickness of 10 mm, and the solid-state electrolyte comprises: aeolian sand 55wt%, silicate cement 20wt%, aluminum oxide fiber 3wt%, sodium sulfate 10wt% and Na3PS4 10wt%, 1.4 Al 0.4 Ti 1.6 (PO4)3 10wt%,

[0048] The method for preparing the energy storage battery is as follows:

[0049] S1: preparing the positive electrode sheet: taking active carbon and sodium carboxymethyl cellulose according to a mass ratio of 93:7, blending the active carbon and sodium carboxymethyl cellulose in NMP, and forming a positive electrode slurry after high-speed stirring, then uniformly coating the positive electrode slurry on a copper foil, and preparing a positive electrode sheet with an active layer thickness of 2 mm after drying, rolling, and slitting;

[0050] S2: preparing a solid electrolyte slurry: taking aeolian sand, portland cement, aluminum silicate fiber, sodium nitrate, and Na 1.4 Al 0.4 Ti 1.6 (PO4)3; putting the aeolian sand, portland cement, aluminum silicate fiber, Na 1.4 Al 0.4 Ti 1.6 (PO4)3 into a mixing container after mixing, and performing dry mixing for 40 min to obtain a uniformly mixed mixture; dissolving the sodium salt in water to obtain a sodium salt solution with a concentration of 0.7 M; adding the mixture into the sodium salt solution, and stirring for 100 min until uniformly dispersed to obtain a slurry;

[0051] S3: preparing the battery: placing the positive electrode sheet and the iron plate in front of and behind the mold respectively, with the positive active layer facing the iron plate; then pouring the slurry into the mold, leveling by vibration, and adjusting the distance between the positive and negative electrode sheets to 20 mm, and then placing the leveled mold in an environment with a temperature of 25°C and a humidity of 50±5% for 15 h; then placing the mold in an environment with a humidity of 90±5% for 7 days to completely hydrate the cement; then drying at 70°C for 4 days and demolding; and placing the demolded product in a 200°C environment for 3 h.

[0052] The battery is tested, and the voltage of the energy storage battery is 1.81 V, the specific energy is 20.9 Wh / Kg, the ionic conductivity is 2.7 mS / cm, and the capacity retention rate after 1000 h is 81%. After standardizing the battery mass, it is calculated that the capacity of the energy storage battery is about 20 Wh.

[0053] Example 4

[0054] An energy storage battery includes a positive electrode sheet, a negative electrode sheet, and a solid electrolyte. The negative electrode sheet is an iron plate with a thickness of 5 mm. The solid electrolyte includes aeolian sand 50 wt%, portland cement 25 wt%, aluminum silicate fiber 5 wt%, sodium nitrate 10 wt%, Na3PS4 5 wt%, and NaFePO4 5 wt%.

[0055] The method for preparing the energy storage battery is as follows:

[0056] S1 preparation of positive electrode sheet: take activated carbon and carboxymethyl cellulose sodium by mass ratio 93:7, blend the activated carbon and carboxymethyl cellulose sodium in NMP, form positive electrode slurry after high-speed stirring, then uniformly coat the positive electrode slurry on copper foil, and after drying, rolling, and slitting, a positive electrode sheet with an active layer thickness of 1 mm is prepared;

[0057] S2 preparation of solid-state electrolyte slurry: take aeolian sand, portland cement, aluminum silicate fiber, sodium nitrate, and Na3PS4, NaFePO4 by proportion; after mixing the aeolian sand, portland cement, aluminum silicate fiber, Na3PS4, and NaFePO4, put them into a mixing container for dry mixing, mix for 40 min to obtain a uniformly mixed mixture; dissolve the sodium salt in water to obtain a 1M sodium salt solution; add the mixture to the sodium salt solution and stir for 100 min until uniformly dispersed to obtain a slurry;

[0058] S3 preparation of battery: place the positive electrode sheet and iron plate in front and back of the mold, respectively, with the positive active layer facing the iron plate; then pour the slurry into the mold, shake and flatten it, and adjust the distance between the positive and negative electrode sheets to 10 mm; then place the shaken and flattened mold in an environment with a temperature of 25°C and a humidity of 50±5% for 15h; then place the mold in an environment with a humidity of 90±5% for 7 days to allow the cement to fully hydrate; then dry at 70°C for 4 days and demold; place the demolded product in a 200°C environment for 3h.

[0059] The battery is tested, and the energy storage battery has a voltage of 1.86V, a specific energy of 21.8Wh / Kg, an ionic conductivity of 3.1mS / cm, and a capacity retention rate of 88% after 1000h. After standardizing the battery mass, it is calculated that the capacity of the energy storage battery is about 21Wh.

[0060] Comparative Example 1

[0061] An energy storage battery includes a positive electrode sheet, a negative electrode sheet, and a solid-state electrolyte. The negative electrode sheet is an iron plate with a thickness of 5mm. The solid-state electrolyte includes aeolian sand 40wt%, sulphate cement 50wt%, and sodium chloride 10wt%. The preparation method of the energy storage battery is as follows:

[0062] S1 preparation of positive electrode sheet: take activated carbon and polyvinylidene fluoride by mass ratio 95:5, blend the activated carbon and polyvinylidene fluoride in NMP, form positive electrode slurry after high-speed stirring, then uniformly coat the positive electrode slurry on copper foil, and after drying, rolling, and slitting, a positive electrode sheet with an active layer thickness of 2mm is prepared;

[0063] S2 preparation of solid electrolyte slurry: wind-blown sand, sulphoaluminate cement, sodium chloride were weighed according to the proportion; the wind-blown sand and sulphoaluminate cement were mixed and then put into a mixing container for dry mixing, and the mixing was carried out for 50 min to obtain a uniformly mixed mixture; sodium chloride was dissolved in water to obtain a 0.1 M sodium salt solution; the mixture was added to the sodium salt solution and stirred for 60 min until uniformly dispersed to obtain a slurry;

[0064] S3 preparation of battery: the positive electrode sheet and the iron plate were placed in front of and behind the mold respectively, with the positive active layer facing the iron plate; then the slurry was poured into the mold, leveled by shaking, and the distance between the positive and negative electrode sheets was adjusted to 20 mm; then the leveled mold was placed in an environment with a temperature of 25°C and a humidity of 50±5% for 10 h; then the mold was placed in an environment with a humidity of 90±5% for 10 days to allow the cement to fully hydrate; then the mold was removed after drying at 80°C for 4 days; the product after demolding was placed at 180°C for 5 h.

[0065] The battery was tested, and the voltage of the energy storage battery was 1.74 V, the specific energy was 13.4 Wh / Kg, the ionic conductivity was 0.7 mS / cm, and the capacity retention rate after 1000 h was 48%. After standardizing the battery mass, it was calculated that the capacity of the energy storage battery was about 13 Wh. However, the battery capacity decays quickly during long-term use, especially during long-term storage at low or high temperatures, and the electrolyte is prone to cracking, which causes problems with the stability of the battery.

[0066] Comparative Example 2

[0067] An energy storage battery, comprising a positive electrode sheet, a negative electrode sheet and a solid electrolyte, the negative electrode sheet is an iron plate with a thickness of 5 mm, and the solid electrolyte comprises: wind-blown sand 70wt%, silicate cement 16wt%, sodium nitrate 10wt% and Na 1.4 Al 0.4 Ti 1.6 (PO4)34wt%,

[0068] The preparation method of the energy storage battery is as follows:

[0069] S1 preparation of positive electrode sheet: active carbon and sodium carboxymethyl cellulose were weighed according to a mass ratio of 93:7, and then added to NMP for blending; after high-speed stirring, a positive electrode slurry was formed; then the positive electrode slurry was uniformly coated on a copper foil, and after drying, rolling, and cutting, a positive electrode sheet with an active layer thickness of 2 mm was prepared;

[0070] S2 preparation of solid electrolyte slurry: wind-blown sand, silicate cement, aluminum silicate fiber, sodium nitrate and Na 1.4 Al 0.4 Ti 1.6(PO4)3; wind-blown sand, Portland cement, aluminum silicate fiber, Na 1.4 Al 0.4 Ti 1.6 (PO4)3mixed and placed in a mixing container for dry mixing, mixed for 40 min, to obtain a uniformly mixed mixture; the sodium salt was dissolved in water to obtain a sodium salt solution with a concentration of 2M; the mixture was added to the sodium salt solution and stirred for 100 min until uniformly dispersed to obtain a slurry;

[0071] S3: battery preparation: placing a positive electrode sheet and an iron plate in front of and behind the mold, respectively, with the positive active layer facing the iron plate; then pouring the slurry into the mold, leveling it by shaking, and adjusting the distance between the positive and negative electrode sheets to 20 mm; then placing the leveled mold in an environment with a temperature of 25°C and a humidity of 50±5% for 15h; then placing the mold in an environment with a humidity of 90±5% for 7 days to allow the cement to fully hydrate; then drying at 70°C for 4 days before demolding; and placing the demolded product in a 200°C environment for 3h.

[0072] The battery was tested, and the energy storage battery had a voltage of 1.77V, a specific energy of 15.3Wh / Kg, an ionic conductivity of 1.2mS / cm, and a capacity retention rate of 51% after 1000h. After standardizing the battery mass, the capacity of the energy storage battery was calculated to be about 15Wh.

[0073] Comparative Example 3

[0074] An energy storage battery comprising a positive electrode sheet, a negative electrode sheet, and a solid-state electrolyte, the negative electrode sheet being an iron plate with a thickness of 5mm, and the solid-state electrolyte comprising: Portland cement 75wt%, aluminum silicate fiber 5wt%, sodium nitrate 10wt%, Na3PS4 5wt%, and NaFePO4 5wt%,

[0075] The energy storage battery was prepared as follows: S1: preparing a positive electrode sheet: taking activated carbon and sodium carboxymethyl cellulose in a mass ratio of 93:7, blending the activated carbon and sodium carboxymethyl cellulose in NMP, and stirring at high speed to form a positive electrode slurry; then uniformly coating the positive electrode slurry on a copper foil, and drying, rolling, and cutting to obtain a positive electrode sheet with an active layer thickness of 1mm;

[0076] S2: preparing a solid-state electrolyte slurry: taking Portland cement, aluminum silicate fiber, sodium nitrate, Na3PS4, and NaFePO4 in the specified proportions; mixing the Portland cement, aluminum silicate fiber, Na3PS4, and NaFePO4, placing them in a mixing container for dry mixing, and mixing for 40 min to obtain a uniformly mixed mixture; dissolving the sodium salt in water to obtain a sodium salt solution with a concentration of 1M; adding the mixture to the sodium salt solution and stirring for 100 min until uniformly dispersed to obtain a slurry;

[0077] S3 Preparation of battery: Place the positive electrode sheet and iron plate in front and back of the mold, respectively, with the positive active layer facing the iron plate. Then pour the slurry into the mold, shake and flatten it, and adjust the distance between the positive and negative electrode sheets to 10 mm. Place the shaken and flattened mold in an environment with a temperature of 25°C and a humidity of 50±5% for 15 hours. Then place the mold in an environment with a humidity of 90±5% for 7 days to allow the cement to fully hydrate. After drying at 70°C for 4 days, remove the mold. Place the demolded product in a 200°C environment for 3 hours.

[0078] The battery was tested, and the energy storage battery had a voltage of 1.79V, a specific energy of 8.6Wh / Kg, an ionic conductivity of 0.4mS / cm, and a capacity retention rate of 36% after 1000 hours of storage. After standardizing the battery mass, the capacity of the energy storage battery was calculated to be about 8Wh.

[0079] Comparative Example 4

[0080] An energy storage battery includes a positive electrode sheet, a negative electrode sheet, and a solid-state electrolyte. The negative electrode sheet is an iron plate with a thickness of 5mm. The solid-state electrolyte includes river sand 50wt%, portland cement 25wt%, aluminum silicate fiber 5wt%, sodium nitrate 10wt%, Na3PS4 5wt%, and NaFePO4 5wt%. The river sand has different particle sizes, with an average particle size of 0.5-3mm.

[0081] The preparation method of the energy storage battery is as follows:

[0082] S1 Preparation of positive electrode sheet: Take active carbon and sodium carboxymethyl cellulose according to a mass ratio of 93:7, and blend them in NMP. After high-speed stirring, a positive electrode slurry is formed. Then the positive electrode slurry is uniformly coated on a copper foil, and after drying, rolling, and cutting, a positive electrode sheet with an active layer thickness of 1mm is obtained.

[0083] S2 Preparation of solid-state electrolyte slurry: Take river sand, portland cement, aluminum silicate fiber, sodium nitrate, Na3PS4, and NaFePO4 according to the proportions. Mix them in a mixing container and dry mix for 40 minutes to obtain a uniformly mixed mixture. Dissolve the sodium salt in water to obtain a 1M sodium salt solution. Add the mixture to the sodium salt solution and stir for 100 minutes until it is evenly dispersed to obtain a slurry.

[0084] S3 Preparation of battery: placing positive electrode sheet and iron plate in front and back of mold respectively, wherein positive active layer is opposite to iron plate; then pouring slurry into mold, shaking and leveling, adjusting distance between positive and negative electrode sheets to 10mm, then placing the shaken and leveled mold in environment with temperature of 25℃ and humidity of 50±5% for 15h; then placing the mold in environment with humidity of 90±5% for 7d to make cement completely hydrated; then drying at 70℃ for 4d and demolding; placing the demolded product in 200℃ for 3h.

[0085] The battery is tested, and the voltage of the energy storage battery is 1.86V, the specific energy is 11.8Wh / Kg, the ionic conductivity is 1.8mS / cm, and the capacity retention rate after 1000h is 76%. After standardizing the battery mass, it is calculated that the capacity of the energy storage battery is about 11Wh.

[0086] From the above test data, it can be seen that the solid-state electrolyte energy storage battery obtained by using aeolian sand, cement, inorganic insulation fiber, sodium salt and additives has high specific energy and ionic conductivity, and the battery has good cycle stability. It can be seen that aeolian sand can be used as electrolyte filler in energy storage battery. The inorganic insulation fiber can effectively improve the stability of the electrolyte, and the electrolyte does not crack or fall off for a long time. However, the amount of aeolian sand cannot be too large, and a large amount of addition will also affect the stability of the solid electrolyte layer. The reason may be that the filler is too much and the solid phase is easy to stratify or precipitate during charging and discharging. It can be seen from the examples and comparative examples 1-2 that aeolian sand can be used in energy storage battery, which will not deteriorate the performance of the battery, and can better control the cost of the battery, and has good economic value. If it can be popularized and used, it can greatly solve the harm caused by desertification and truly turn waste into treasure. It can be seen from comparative example 3 that the performance of the cement battery without using aeolian sand is reduced more obviously. After analysis, it may be that the cement content is high and there is no filler in the electrolyte, the viscosity of the cement slurry is high, and the additives are difficult to disperse uniformly, which greatly reduces the internal ion transmission channel and affects ion transmission. It can be seen from comparative example 4 of river sand that the cement and inorganic fiber system using aeolian sand has high specific energy and ionic conductivity. Analysis may be that the specific system produces sufficient internal pores, providing rich channels for ion transmission.

[0087] The above describes in detail the energy storage battery and the preparation method thereof, and the above content is a further detailed description of the present application in combination with specific preferred embodiments, and cannot be regarded as the specific implementation of the present application being limited to these descriptions. For ordinary skilled persons in the technical field of the present application, the architecture form can be flexible and changeable without departing from the concept of the present application, and a series of products can be derived. Any simple deduction or replacement should be regarded as belonging to the patent protection range determined by the submitted claims of the present application.

Claims

1. An energy storage battery comprising a positive electrode sheet, a negative electrode sheet, and a solid-state electrolyte separating the positive electrode sheet and the negative electrode sheet, characterized by, The solid-state electrolyte comprises: aeolian sand, cement, inorganic insulating fiber, a sodium salt, and an additive selected from at least one of Na3Zr2Si2PO 12 , Na3Zr2Si3P3O 14 , Li7La3Zr2O 12 , Li 6.4 La3Zr 1.4 Ta 0.6 O 12 , NaFePO4, Na3PS4, Na3PSe4, Na 10 SnP2S 12 , Na 1.4 Al 0.4 Ti 1.6 (PO4)3, and Na 0.5 Bi 0.5 TiO3 The inorganic insulating fiber is selected from at least one of alkali-free glass fiber, alumina fiber, basalt fiber, mullite fiber, and aluminum silicate fiber, and the cement is one of sulphoaluminate cement or portland cement; The mass fraction of each component in the solid-state electrolyte is 40-60wt% of aeolian sand, 20-40wt% of cement, 1-5wt% of inorganic insulating fiber, 1-10wt% of sodium salt, and 5-10wt% of additive.

2. The energy storage cell of claim 1, wherein, The positive electrode tab includes a positive electrode current collector and a positive electrode active layer attached to the positive electrode current collector, the positive electrode active layer includes 90wt%-95wt% of activated carbon and 5wt%-10wt% of a binder selected from one of polytetrafluoroethylene, polyvinylidene fluoride, and sodium carboxymethyl cellulose, the positive electrode active layer has a thickness of 0.5-3mm, and the positive electrode current collector is a copper foil or an aluminum foil.

3. The energy storage cell of claim 1, wherein, The negative electrode tab is a metal plate, and the metal is selected from one of iron and zinc, and the metal plate has a thickness of 1-10mm.

4. The energy storage cell of claim 1, wherein, The positive electrode tab is prepared by weighing activated carbon and a binder in a mass ratio of 90-95:5-10, blending the activated carbon and the binder in an organic solvent NMP, forming a positive electrode slurry after high-speed stirring, uniformly coating the positive electrode slurry on a positive electrode current collector, and obtaining the positive electrode tab after drying, rolling, and slitting.

5. The energy storage cell of claim 1, wherein, The solid-state electrolyte has a thickness of 5-50mm, the sodium salt is one of sodium nitrate and sodium sulfate, and the solid-state electrolyte is prepared by the following method: 1) weighing aeolian sand, cement, inorganic insulating fiber, sodium salt, and additive according to a proportion; 2) mixing the aeolian sand, cement, inorganic insulating fiber, and additive, placing the mixture in a mixing container for dry mixing, and mixing for 10-60min to obtain a uniformly mixed mixture; dissolving the sodium salt in water to obtain a sodium salt solution with a concentration of 0.5-1M; 3) adding the mixture obtained in step 2) to the sodium salt solution, stirring for 60-200min until the mixture is uniformly dispersed to obtain a slurry, pouring the slurry into a mold, vibrating and smoothing the slurry, and curing and heat treating the slurry to obtain the solid-state electrolyte.

6. The energy storage cell of claim 5, wherein, The curing specifically includes placing the vibrated and smoothed mold in an environment with a temperature of 25℃ and a humidity of 50±5% for 10-20h, then placing the mold in an environment with a humidity of 90±5% for 5-10 days to completely hydrate the cement, then drying the mold at 60-80℃ for 2-5 days to remove the mold, and the heat treatment includes placing the removed product in an environment with a temperature of 150-250℃ for 1-5h.

7. A method of making an energy storage cell as claimed in any one of claims 1 to 6, the energy storage cell comprising a positive electrode sheet, a negative electrode sheet and a solid state electrolyte located between and separating the positive electrode sheet and the negative electrode sheet, characterised in that, The method includes the following steps: S1 preparing a positive electrode tab: weighing activated carbon and a binder in a mass ratio of 90-95:5-10, blending the activated carbon and the binder in NMP, forming a positive electrode slurry after high-speed stirring, uniformly coating the positive electrode slurry on a positive electrode current collector, and obtaining the positive electrode tab after drying, rolling, and slitting; S2: preparing a solid electrolyte slurry: taking aeolian sand, cement, inorganic insulating fiber, sodium salt and additives by proportion; mixing the aeolian sand, cement, inorganic insulating fiber and additives, and then putting them into a mixing container for dry mixing for 10-60 min to obtain a mixed material with uniform mixing; dissolving the sodium salt in water to obtain a sodium salt solution with a concentration of 0.5-1 M; adding the mixed material into the sodium salt solution, and stirring for 60-200 min until uniformly dispersed to obtain a slurry; S3: preparing a battery: placing a positive electrode sheet and a negative electrode sheet in front of and behind a mold respectively, wherein the positive active layer is opposite to the negative electrode sheet; then pouring the slurry into the mold, and leveling by vibration, adjusting the distance between the positive and negative electrode sheets, and then solidifying and heat treating to obtain the battery.

8. The production method according to claim 7, characterized by, The solidification is specifically: placing the mold leveled by vibration in an environment with a temperature of 25°C and a humidity of 50±5% for 10-20 h; then placing the mold in an environment with a humidity of 90±5% for curing for 5-10 days, so that the cement is completely hydrated; then placing the mold in a drying environment with a temperature of 60-80°C for 2-5 days for demolding; and the heat treatment is placing the demolded product in a static environment with a temperature of 150-250°C for 1-5 h.