Solid-state lead-acid storage battery based on curved graphene

Abstract

The invention provides a solid-state lead-acid storage battery based on curved-surface graphene, and relates to the technical field of batteries, the solid-state lead-acid storage battery comprises a positive plate, a negative plate and a solid-state electrolyte, the positive plate uses lead dioxide as an active substance, and is in contact with the solid-state electrolyte to complete an oxidation reaction; the negative plate adopts metal lead Pb to participate in the reduction reaction; according to the solid electrolyte, lithium carbosilicate-based gel is adopted as electrolyte, and an ion conduction channel is provided, so that effective charge transfer is carried out between a positive electrode and a negative electrode; according to the invention, lead Pb is used as a negative electrode, lead dioxide is used as a positive electrode, lithium carbosilicate is used as an electrolyte, the curved graphene with a specific quantum effect is added into the positive and negative electrode plates, and the electrode reaction kinetics is optimized by using the curved shell structure and the high specific surface area characteristic of the curved graphene, so that the energy conversion efficiency of the battery is improved from 35%-55% traditionally to 70%-99% or above.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of battery, especially to a solid-state lead-acid battery based on curved graphene. BACKGROUND

[0002] As the most widely used electrochemical device in the field of energy storage, lead-acid battery is a secondary battery system with lead-based alloy as the grid frame, lead dioxide as the positive active material, and sponge lead as the negative active material, and ion conduction is realized through sulfuric acid solution. It specifically includes: adopting valve control sealing design (VRLA) or ultra-fine glass fiber separator (AGM) to realize electrolyte immobilization, improving corrosion resistance through lead-calcium-tin multi-element alloy grid, optimizing power density relying on bipolar plate series structure, and forming a stable voltage output platform of 2.0V per cell. This classic structure makes it dominate in the fields of automobile starting power supply, communication base station standby power supply, etc. However, due to the physical properties of traditional liquid electrolyte, there are technical bottlenecks such as electrolyte leakage risk, high interface ion transmission impedance, and short deep charge-discharge cycle life.

[0003] The existing lead-acid battery technology has four major defects: first, the liquid sulfuric acid electrolyte needs to be recycled through a special valve, but the electrolytic water side reaction at the end of charging will still cause water loss, increased internal resistance, and capacity decay; second, the lead sulfate crystal deposition at the interface between the positive and negative plates and the electrolyte forms a high impedance layer, resulting in low efficiency of large current charge and discharge, especially in low temperature environment; third, the theoretical specific capacity of lead-based active material is only about 50mAh / g, which makes the mass energy density long-term hovering in the range of 30-50Wh / kg, making it difficult to meet the demand for energy density of portable devices and electric vehicles; fourth, the traditional manufacturing process relies on complex processes such as plate slitting and busbar welding, which not only leads to low production efficiency, but also easily causes battery failure due to welding defects, thus restricting the cost control of large-scale application. Therefore, the present application proposes a solid-state lead-acid battery based on curved graphene to solve the problems existing in the prior art. SUMMARY

[0004] To solve the above problems, the present application provides a solid-state lead-acid battery based on curved graphene, which uses a gel solid-state electrolyte formed by a curved graphene and silicon composite to solve the many shortcomings of traditional liquid lead-acid batteries, and has the characteristics of high safety, high capacity ratio, long life and low cost.

[0005] To achieve the purpose of the present application, the present application realizes the following technical scheme: a solid-state lead-acid battery based on curved graphene, comprising a positive plate, a negative plate and a solid-state electrolyte, the positive plate uses lead dioxide As an active material, it contacts with the solid-state electrolyte to complete the oxidation reaction.

[0006] The negative plate uses metal lead Pb to participate in the reduction reaction.

[0007] The solid-state electrolyte uses carbon lithium silicate The base gel is used as an electrolyte to provide an ion conduction channel to enable effective charge transfer between the positive and negative electrodes.

[0008] Further improvement lies in that the negative plate comprises the following components by mass ratio: 1000 parts of Pb lead powder, 5-50 parts of curved graphene powder, 1-8 parts of BaSO4, 5-12 parts of HA humic acid, 0.5-3 parts of VANISPERSE A sodium lignosulfonate, 0.1-0.3 parts of PP fiber, 1-5 g of wood powder, 160-180 parts of H2SO4 sulfuric acid, and 50-80 parts of deionized water.

[0009] Further improvement lies in that the Pb lead powder has a particle size of 250-300 mesh, an apparent density of 1.75-2 g / cm, an oxidation degree of 65-85%, and a water absorption of 110-140 g / kg; the curved graphene powder has a particle size of 6Å-9Å, an electromotive force of 300-500 mv, 2-5 layers of graphene sheets, a sheet diameter of >1 um, and an oxygen content of 35-60% on the surface of the graphene sheet structure; the BaSO4 is 180 mesh; the wood powder is 200-300 mesh; and the H2SO4 sulfuric acid has a density of 1.14±0.005 at 25℃.

[0010] Further improvement lies in that the preparation process of the negative plate comprises the following steps:

[0011] Negative paste preparation: pour H2SO4 sulfuric acid with a density of 1.14±0.005 at 25℃ into a blender, slowly add other negative formula mixed powder while stirring, then add curved graphene and deionized water after stirring for 10 min, stir for 45 min, and adjust the paste according to the dry and wet conditions using deionized water, and control the apparent density of the lead paste to be 380-400 g / cm;

[0012] Negative coating: place 2-3 layers of glass cloth on the coating workbench and place the grid on it, use a coating knife to coat the lead paste into the grid mesh, cover 1-2 layers of glass cloth after coating, and repeatedly roll with a roller for 3-4 times, then turn the electrode over by 180°, and coat the paste again in the same way as above;

[0013] Negative drying: place or hang the coated electrode in the oven at 50-65℃ to dry to a dryness of 50%;

[0014] Pickling: soak in H2SO4 sulfuric acid with D=1.14±0.005 at 25℃ for 2-3h, then take out the negative electrode and place it on the workbench, cover it with a layer of glass cloth and a partition, stack it to the set height in the same way, and keep it in the air or in an oven at 50-65℃ for 15-20h, then take out the electrode and dry it until it is completely dry.

[0015] Further improvement lies in that the positive plate comprises the following mass ratio components: 1000 parts of Pb lead powder, 10-100 parts of curved graphene powder, 1-5 parts of CMC sodium carboxymethyl cellulose, 0.1-1 part of NANO SIO2(50nm), 0.5-5 parts of NaSO4, 0.5-5 parts of CoSO4, 0.1-0.5 parts of PP fiber, 0.5-2 parts of H2SIF6 silicon fluoride acid, 70-80 parts of H2SO4 sulfuric acid, and 100-120 parts of deionized water.

[0016] Further improvement lies in that the particle size of the Pb lead powder is 250-300 mesh, the apparent density is 1.75-2g / cm, the oxidation degree is 65-85%, and the water absorption is 110-140g / kg; the particle size of the curved graphene powder is 6Å-9Å, the electromotive force is 300-500mv, the olefin sheet is 2-5 layers, the sheet diameter is >1um, and the oxygen content on the surface of the olefin sheet structure is 35-60%; both NaSO4 and CoSO4 are 180 mesh; and the H2SO4 sulfuric acid is 25℃ d=1.40.

[0017] Further improvement lies in that the preparation process of the positive plate comprises the following steps:

[0018] Positive paste mixing: mix the Pb lead powder, the curved graphene powder, the CMC sodium carboxymethyl cellulose, the NANO SIO2(50nm), the NaSO4, the CoSO4, and the PP fiber uniformly into a mixed powder, mix the H2SO4 sulfuric acid and the deionized water uniformly, then pour them into a blender, add the mixed powder while stirring, stir for 10min, then add the H2SO4 sulfuric acid with a specific gravity of 1.40 into the blender, stir for 45min, adjust the deionized water according to the dry and wet conditions, and make the apparent density of the lead paste 340-355g / cm.

[0019] Positive coating: pad 2-3 layers of glass cloth on the coating workbench and place the grid on it, use a coating knife to coat the lead paste into the grid mesh, cover it with 1-2 layers of glass cloth, roll it repeatedly for 3-4 times with a roller, then turn the electrode over by 180°, and coat the paste again in the same way as above.

[0020] Drying: place or hang the coated electrode in the oven at 50-65℃ to dry to a dryness of 50%;

[0021] Pickling: soak in sulfuric acid solution with D=1.20 at 25℃ for 2-3h, then take out and drip dry the acid solution, dry in an oven at 50-65℃ until dry.

[0022] Further improvement lies in that the solid-state electrolyte comprises the following mass ratio components: 20-40 parts of curved graphene, 60-80 parts of fumed silica , 1-5 parts of lithium silicate , 1-10 parts of H2SO4 sulfuric acid.

[0023] Further improvement lies in that the particle size of the curved graphene is 6-9Å, the electromotive force is 300-500mv, the number of layers of the graphene sheet is 2-5, the sheet diameter is >1um, and the oxygen content on the surface of the graphene sheet structure is 35-60%; the H2SO4 sulfuric acid is D=1.14±0.005 at 25℃.

[0024] Further improvement lies in that the preparation process of the solid-state electrolyte comprises the following steps:

[0025] The weighed fumed silica is added to an organic solvent, and ultrasonic dispersion equipment is used for ultrasonic dispersion treatment for about 30-60min, so that the fumed silica is uniformly dispersed in the organic solvent to form a uniform suspension;

[0026] The weighed curved graphene is slowly added to the above suspension, and ultrasonic dispersion is continued for 60-120min to ensure that the curved graphene and the fumed silica are fully mixed and uniform, forming a mixed dispersion liquid;

[0027] The weighed lithium silicate is added to the above mixed dispersion liquid, and high-speed stirring equipment is used for stirring at a stirring speed of 500-1000r / min for 60-120min, so that the lithium silicate is uniformly dissolved and dispersed in the mixed system;

[0028] Under stirring, H2SO4 sulfuric acid is slowly added to the above mixed system, and the dropping speed is controlled to be slow and uniform, while the temperature and state changes of the system are observed, the stirring is maintained during the dropping process, and after the dropping is completed, the stirring is continued for 30-60min, so that the sulfuric acid and other components are fully reacted and mixed;

[0029] The above mixed solution is transferred to a vacuum drying box, and vacuum drying treatment is carried out at a temperature of 60-80℃ until the organic solvent is completely volatilized and removed;

[0030] The dried solid mixture is ground to make its particles finer and more uniform, and then, as needed, it is made into a solid electrolyte of the required shape and size by hot pressing or cold pressing.

[0031] The entire preparation process is carried out in a dry and clean environment.

[0032] The beneficial effects of this invention are as follows:

[0033] 1. This invention uses lead (Pb) as the negative electrode and lead dioxide as the negative electrode. Lithium carbosilicate is the positive electrode. As an electrolyte, curved graphene with specific quantum effects (particle size 6Å-9Å, electromotive force 300-500mV, 2-5 layers of graphene sheets, etc.) is added to the positive and negative electrode plates. By utilizing its curved shell structure and high specific surface area, the electrode reaction kinetics are optimized, which increases the battery energy conversion efficiency from the traditional 35%-55% to more than 70%-99%, and achieves a significant improvement in theoretical capacity utilization.

[0034] 2. This invention uses a carbon-silicon composite material (lithium carbon silicate). Solid electrolytes are prepared by using silicon as a base gel. The ultra-high theoretical specific capacity of silicon (4200mAh / g) and the three-dimensional network structure formed by curved graphene are used to construct channels with high ionic conductivity. At the same time, the directional movement of lithium ions in the crystal structure ensures the ion conduction efficiency during charging and discharging.

[0035] 3. The solid electrolyte of the present invention forms a good interface match with the positive and negative electrode materials, reduces the electrode / electrolyte interface impedance, reduces charge transfer resistance, and at the same time utilizes the oxygen-containing groups on the surface of curved graphene to improve interface wettability and enhance electrochemical stability.

[0036] 4. This invention achieves lightweight battery design by combining the lightweight and high-strength properties of curved graphene with the three-dimensional network structure of solid electrolyte. By combining the high specific capacity of silicon-based materials with the high specific surface area of ​​graphene, the energy density per unit volume / weight is increased, while extending cycle life and meeting the requirements for high-capacity and long-life energy storage.

[0037] 5. This invention replaces traditional liquid sulfuric acid with a solid electrolyte, eliminating the risk of leakage and improving battery safety; combining the stable structure of curved graphene with the electrochemical stability of solid electrolyte reduces the probability of thermal runaway, while optimizing the production process and reducing manufacturing costs, thus combining economic efficiency and environmental friendliness. Detailed Implementation

[0038] To enhance understanding of the present invention, the present invention will be further described in detail below with reference to embodiments. These embodiments are only used to explain the present invention and do not constitute a limitation on the scope of protection of the present invention.

[0039] Example 1

[0040] This embodiment proposes a solid-state lead-acid battery based on curved graphene, including a positive electrode plate, a negative electrode plate, and a solid electrolyte.

[0041] Positive electrode plate: using lead dioxide ( As an active substance, it comes into contact with the solid electrolyte to complete the oxidation reaction.

[0042] Negative electrode plate: metallic lead (Pb) is used to participate in the reduction reaction.

[0043] Solid electrolyte: The electrolyte is lithium carbosilicate (LiSiO2) A gel-based solid electrolyte that replaces traditional liquid sulfuric acid solution and provides ion conduction channels.

[0044] The redox reactions of the positive and negative electrode active materials during charging and discharging are briefly described below:

[0045] Discharge process

[0046] Negative electrode reaction: Lead (Pb) at the negative electrode loses electrons and undergoes an oxidation reaction to generate lead ions (Pb). 2＋ ), lead ions and sulfate ions in the gel electrolyte ( ) combine to form lead sulfate ( The electrode reaction formula is: At this time, lithium ions in the solid electrolyte ( They will move towards the negative electrode and may form some ion adsorption layers on the negative electrode surface together with sulfate ions or participate in some surface chemical reactions. This will have a certain impact on the reaction kinetics and electrode interface properties of the negative electrode, help stabilize the charge distribution and reaction environment on the electrode surface, and promote the smooth progress of the reaction.

[0047] Positive electrode reaction: Lead dioxide at the positive electrode ( In the presence of sulfuric acid, lead gains electrons and undergoes a reduction reaction, initially producing divalent lead ions (Pb). 2＋ Then, divalent lead ions combine with sulfate ions to form lead sulfate ( ). Simultaneously, water is generated, and the electrode reaction equation is: In this process, lithium ions previously embedded in the cathode material ( It will detach from the crystal lattice and return to the solid electrolyte to participate in the ion conduction process, providing an ion conduction pathway for electron transfer and reaction, and maintaining the charge balance inside the battery.

[0048] Overall reaction: The overall reaction during battery discharge is as follows In this process, chemical energy is converted into electrical energy, and electrons flow from the negative electrode to the positive electrode through the external circuit to form an electric current.

[0049] Charging process

[0050] Negative electrode reaction: Lead sulfate (PbSO4) at the negative electrode gains electrons and undergoes a reduction reaction, regenerating lead (Pb) and sulfate ions (PbSO4). The electrode reaction formula is: Lithium-ion ( In this process, lithium ions generally do not directly participate in the oxidation reaction of lead. However, due to the change in the electric field on the surface of the negative electrode and the diffusion of ions, lithium ions will also be distributed and adjusted in the solid electrolyte region near the negative electrode. They may form some local ion pairs or weak interactions with sulfate ions, which will affect the transport and distribution of ions.

[0051] Positive electrode reaction: Lead sulfate at the positive electrode ( In the presence of water, it loses electrons and undergoes an oxidation reaction, producing lead dioxide (PbO2) and hydrogen ions (H+). ＋ ) and sulfate ions ( The electrode reaction formula is: Meanwhile, lithium ions in the solid electrolyte ( Due to the electric field, it will move towards the positive electrode and may be embedded in the lattice of lead dioxide or its reaction intermediates to form lithium-containing compounds or solid solutions, thereby changing the structure and properties of the electrode material to a certain extent, which helps to improve the conductivity and reactivity of the electrode and promotes the reaction.

[0052] Overall reaction: The overall reaction during charging is Electrical energy is converted into chemical energy and stored, restoring the battery to its state before discharge.

[0053] Throughout the entire charge and discharge process, in the solid electrolyte (lithium carbosilicate ( Lithium ions can move within the channels of the crystal structure, providing ion transport paths for battery chemical reactions, enabling effective charge transfer between the positive and negative electrodes, and completing the battery's charging and discharging process.

[0054] The basic structure of the solid-state lead-acid battery is similar to that of the traditional lead-acid battery, and lead is used as the negative electrode and lead dioxide is used as the positive electrode, but different proportions of curved graphene are added as the electrolyte and are solidified and replaced by solid-state materials in the positive and negative plates. The substances participating in the electrode reaction in the solid-state lead-acid battery are the sponge metal lead of the negative electrode, lead sulfate, the lead dioxide of the positive electrode, lead sulfate, the sulfuric acid in the electrolyte, and water, which are all active substances. The reaction of the active substances stores and releases electrical energy. The utilization rate of the active substances becomes an important indicator of the lead-acid battery, which is the ratio of the actual capacity to the theoretical capacity of the active substances on the electrode. The theoretical capacity is calculated according to Faraday's law. In these energy conversion processes, the conversion efficiency calculated by the actual capacity and the theoretical capacity is in the range of 35%-55%.

[0055] The present application utilizes the special quantum effect of curved graphene material to implement different preparation and compatibility methods for the positive and negative plates of various types of batteries and solid-state electrolytes, which can increase the conversion efficiency of the lead-acid battery to more than 70%-99%. This makes it possible to achieve lightweight, high capacity, long life, and high performance of the battery.

[0056] According to the specific carbon structure of the present application, the curved graphene shell structure is characterized by a particle size of 6-9 Å, an electromotive force of 300-500 mv, an olefin sheet of 2-5 layers, a sheet diameter of >1 um, an oxygen content of 35-60 percent on the surface of the olefin sheet structure, and different shell structures. The unique characteristics and specific components of this material are applied to batteries, especially solid-state electrolytes prepared from carbon-silicon composite materials. Silicon has an ultra-high theoretical specific capacity of up to 4200 mAh / g, and curved graphene has a very large specific surface area. Theoretically, the specific surface area of a single-layer graphene can reach 2630 square meters per gram. The carbon-silicon composite forms a three-dimensional network structure to form good interface compatibility, high ionic conductivity, and excellent electrochemical stability. This mechanism can be applied to various types of batteries such as acid batteries, alkaline batteries, and air batteries.

[0057] Example Two

[0058] The present embodiment proposes a solid-state lead-acid battery based on curved graphene, including the following preparation methods:

[0059] The negative plate includes the following mass ratio components: 1000 parts of Pb lead powder, 5-50 parts of curved graphene powder, 1-8 parts of BaSO4, 5-12 parts of HA humic acid, 0.5-3 parts of VANISPERSE A sodium lignosulfonate, 0.1-0.3 parts of PP fiber, 1-5 g of wood powder, 160-180 parts of H2SO4 sulfuric acid, and 50-80 parts of deionized water.

[0060] Pb lead powder particle size 250-300 mesh, apparent density 1.75-2 g / cm, oxidation degree 65-85%, water absorption 110-140 g / kg; curved graphene powder particle size 6Å-9Å, electromotive force 300-500 mv, ene sheet 2-5 layers, sheet diameter >1 um, ene sheet structure surface oxygen content 35-60 percent; BaSO4 180 mesh; wood powder 200-300 mesh; H2SO4 sulfuric acid 25℃ D=1.14±0.005.

[0061] Positive plate: including the following mass ratio components: 1000 parts Pb lead powder, 10-100 parts curved graphene powder, 1-5 parts CMC sodium carboxymethyl cellulose, 0.1-1 parts NANO SIO2(50 nm), 0.5-5 parts NaSO4, 0.5-5 parts CoSO4, 0.1-0.5 parts PP fiber, 0.5-2 parts H2SIF6 silicon fluoride acid, 70-80 parts H2SO4 sulfuric acid, 100-120 parts deionized water.

[0062] Pb lead powder particle size 250-300 mesh, apparent density 1.75-2 g / cm, oxidation degree 65-85%, water absorption 110-140 g / kg; curved graphene powder particle size 6Å-9Å, electromotive force 300-500 mv, ene sheet 2-5 layers, sheet diameter >1 um, ene sheet structure surface oxygen content 35-60 percent; NaSO4 and CoSO4 are both 180 mesh; H2SO4 sulfuric acid 25℃ d=1.40.

[0063] Solid-state electrolyte: the preparation method is to add 1-10 percent of the mass of the electrolyte in the sulfuric acid electrolyte with 25℃ D=1.285±0.005, including the following mass ratio components: 20-40 parts curved graphene, 60-80 parts fumed silica , 1-5 parts lithium silicate , 1-10 parts H2SO4 sulfuric acid.

[0064] Curved graphene particle size 6Å-9Å, electromotive force 300-500 mv, ene sheet 2-5 layers, sheet diameter >1 um, ene sheet structure surface oxygen content 35-60 percent; H2SO4 sulfuric acid 25℃ D=1.14±0.005.

[0065] Preparation process

[0066] Negative electrode:

[0067] Negative paste: First, pour the sulfuric acid solution with D = 1.14 ± 0.005 at 25°C into the blender, slowly add the negative formula mixed powder while stirring, after stirring for 10 minutes, add the curved graphene and deionized water, and stir for 45 minutes. According to the dry and wet conditions, deionized water can be used for adjustment. The density of the lead paste is 380-400 g / cm.

[0068] Negative coating: same as the positive coating process.

[0069] Negative drying to 50%: same as the positive drying to 50% process.

[0070] Acid immersion: soak in sulfuric acid solution with D = 1.14 ± 0.005 at 25°C for 2-3h, then take out the negative electrode and place it on the workbench, cover it with a layer of glass cloth and a spacer, stack it to a certain height according to the same method, and solidify in air or in an oven at 50-65°C for 15-20h. Then take out the electrode and dry it until it is completely dry.

[0071] Positive:

[0072] Positive paste: Mix ①-⑦ formulations uniformly for standby. Mix ⑨ and ⑩ uniformly, then pour into the blender, add ①-⑦ mixed powder while stirring, after stirring for 10 minutes, add ⑧ sulfuric acid solution with a specific gravity of 1.40 into the blender, stir for about 45 minutes. According to the dry and wet conditions, deionized water can be used for adjustment. The density of the lead paste is 340-355 g / cm.

[0073] Positive coating: Place 2-3 layers of glass cloth on the coating workbench and place the grid on it. Use a coating knife to coat the lead paste into the grid mesh, cover it with 1-2 layers of glass cloth (or use 511 nylon cloth) after coating, roll it repeatedly for 3-4 times, then turn the electrode over 180°, and coat it again in the same way as above. Remember to coat evenly.

[0074] Drying: Place or hang the coated electrode in the oven at 50-65°C to dry to 50% dryness.

[0075] Acid immersion: soak in sulfuric acid solution with D = 1.20 ± at 25°C for 2-3h, then take out and drip dry the acid solution, and dry it in an oven at 50-65°C until it is completely dry.

[0076] Solid-state electrolyte:

[0077] Curved graphene: select curved graphene with particle size of 6Å-9Å, electromotive force of 300-500mV, olefin sheet of 2-5 layers, sheet diameter greater than 1μm, and oxygen content on the surface of the olefin sheet structure of 35%-60%, and take 20%-40% of the amount according to the formula proportion.

[0078] Fumed silica: Select fumed silica with a particle size of 50-100 nm, and take 60-80% of the amount.

[0079] Lithium silicate: Take 1-5% of lithium silicate.

[0080] Sulfuric acid: Prepare sulfuric acid with a density D = 1.14 ± 0.005 at 25°C, and take 1-10% of the amount.

[0081] Add the weighed fumed silica to an appropriate amount of organic solvent (such as anhydrous ethanol), and use ultrasonic dispersion equipment for ultrasonic dispersion treatment, with an ultrasonic time of about 30-60 minutes. This allows the fumed silica to be uniformly dispersed in the organic solvent, forming a uniform suspension.

[0082] Next, slowly add the weighed curved graphene to the above suspension, and continue ultrasonic dispersion for 60-120 minutes to ensure that the curved graphene and fumed silica are fully mixed and uniform, forming a mixed dispersion. This step utilizes the cavitation effect of ultrasound to fully disperse the particles and prevent agglomeration.

[0083] Add the weighed lithium silicate to the above mixed dispersion, and use high-speed stirring equipment for stirring, with a stirring speed controlled at 500-1000 revolutions per minute and a stirring time of 60-120 minutes. This allows the lithium silicate to be uniformly dissolved and dispersed in the mixed system. The addition of lithium silicate helps to improve the ionic conductivity and chemical stability of the electrolyte.

[0084] Dropwise addition of sulfuric acid: Slowly add sulfuric acid to the above mixed system under stirring. The dropping speed should be slow and uniform, while closely observing the temperature and state changes of the system. Maintain stirring during the dropping process, and continue stirring for 30-60 minutes after the dropping is completed to allow the sulfuric acid to fully react and mix with other components. Sulfuric acid participates in the formation of ion conduction channels in the electrolyte.

[0085] Removal of organic solvent: Transfer the above mixed solution to a vacuum drying oven, and perform vacuum drying treatment at a temperature of 60-80°C until the organic solvent is completely volatilized and removed. The drying time depends on the amount of solution and the performance of the drying equipment, and generally requires several hours to several dozen hours.

[0086] Forming treatment: Grind the dried solid mixture to make the particles smaller and more uniform. Then, according to the needs, use hot pressing or cold pressing methods to make it into a solid electrolyte with the required shape and size. When hot pressing, the temperature is generally controlled at 100-200°C, the pressure is 10-50 MPa, and the holding time is certain; cold pressing is performed at room temperature with appropriate pressure.

[0087] Environmental control: The entire preparation process is carried out in a dry and clean environment to avoid the introduction of moisture and impurities, which affect the performance of the electrolyte.

[0088] Process parameter control: Strictly control the temperature, time, stirring speed and other parameters of each process step to ensure that the prepared solid-state electrolyte has stable performance.

[0089] The solid-state lead-acid battery based on curved graphene uses lead Pb as the negative electrode, lead dioxide PbO2 as the positive electrode, carbon silicon lithium silicate as the electrolyte. A specific amount of curved graphene with quantum effect (particle size 6Å-9Å, electromotive force 300-500mV, 2-5 layers of graphene sheets, etc.) is added to the positive and negative electrode plates. The curved shell structure and high specific surface area characteristics of the curved graphene are used to optimize the electrode reaction kinetics, so that the battery energy conversion efficiency is increased from the traditional 35%-55% to more than 70%-99%, and the theoretical capacity utilization rate is significantly improved. The solid-state electrolyte is prepared using carbon silicon composite (carbon silicon lithium silicate gel). The three-dimensional network structure formed by silicon with ultra-high theoretical specific capacity (4200mAh / g) and curved graphene is used to construct a high ionic conductivity channel, and the directional movement of lithium ions in the crystal structure is used to ensure the ion conduction efficiency during charging and discharging. At the same time, the solid-state electrolyte of the present application forms a good interface matching with the positive and negative electrode materials, reduces the electrode / electrolyte interface impedance, reduces the charge transfer resistance, and improves the interfacial wettability and electrochemical stability by using the oxygen-containing groups on the surface of the curved graphene. In addition, the light weight and high strength characteristics of the curved graphene and the three-dimensional network structure of the solid-state electrolyte are used to realize the lightweight design of the battery, and the high specific capacity of the silicon-based material and the high specific surface area of the graphene are combined to improve the energy density per unit volume / weight, prolong the cycle life, and meet the high-capacity and long-life energy storage requirements. Finally, the solid-state electrolyte is used to replace the traditional liquid sulfuric acid to eliminate the risk of liquid leakage and improve the safety of the battery; the stable structure of the curved graphene and the electrochemical stability of the solid-state electrolyte are combined to reduce the probability of thermal runaway, and the production process is optimized to reduce the manufacturing cost, which is economical and environmentally friendly.

[0090] The above shows and describes the basic principles, main features and advantages of the present application. Those skilled in the art should understand that the present application is not limited to the above examples, and the above examples and descriptions in the specification are only to illustrate the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application. The scope of protection of the present application is defined by the appended claims and their equivalents.

Claims

1. A curved graphene based solid state lead acid battery comprising positive plates, negative plates and a solid state electrolyte characterised in that: The positive plate uses lead dioxide As an active material, it contacts with solid electrolyte and completes oxidation reaction; The negative plate adopts metal lead Pb to participate in the reduction reaction. The solid-state electrolyte employs carbon lithium silicate The base gel serves as an electrolyte, providing an ion conduction path for effective charge transfer between the positive and negative electrodes.

2. A solid state lead-acid battery based on curved graphene according to claim 1, characterized in that: The negative plate comprises the following components in mass ratio: 1000 parts of Pb powder, 5-50 parts of curved surface graphene powder, 1-8 parts of BaSO4, 5-12 parts of HA humic acid, 0.5-3 parts of VANISPERSE A sodium lignosulfonate, 0.1-0.3 parts of PP fiber, 1-5 parts of wood powder, 160-180 parts of H2SO4 sulfuric acid, and 50-80 parts of deionized water.

3. A curved graphene based solid state lead-acid battery as claimed in claim 2, wherein: The particle size of the Pb powder is 250-300 mesh, the apparent density is 1.75-2 g / cm, the oxidation degree is 65-85%, and the water absorption is 110-140 g / kg; the particle size of the curved surface graphene powder is 6-9 Å, the electromotive force is 300-500 mv, the number of layers of the graphene sheet is 2-5, the sheet diameter is >1 um, and the oxygen content on the surface of the graphene sheet structure is 35-60%; the BaSO4 is 180 mesh; the wood powder is 200-300 mesh; and the H2SO4 sulfuric acid is 25 DEG C D=1.14+ / -0.

005.

4. A solid state lead-acid battery based on curved graphene according to claim 3, characterized in that: The preparation process of the negative plate comprises the following steps: Negative paste preparation: pour the H2SO4 sulfuric acid with 25 DEG C D=1.14+ / -0.005 into a blender, slowly add other negative formula mixed powder while stirring, then add the curved surface graphene and deionized water after stirring for 10 min, stir for 45 min, and adjust according to the dry and wet conditions, and control the lead paste apparent density to be 380-400 g / cm; Negative coating: pad 2-3 layers of glass cloth on the coating workbench, place the grid on the glass cloth, coat the lead paste into the grid mesh with a coating knife, cover 1-2 layers of glass cloth after coating, repeatedly roll with a roller for 3-4 times, then turn the electrode over by 180 DEG, and coat again in the same way as above; Negative drying: place or hang the coated electrode in the oven, and dry at 50-65 DEG C until the dryness degree is 50%; Acid immersion: immerse in the H2SO4 sulfuric acid with 25 DEG C D=1.14+ / -0.005 for 2-3 h, then take out the negative electrode and place it on the workbench, cover a layer of glass cloth and a spacer, stack and set the height in the same way, and solidify in the air or in the oven at 50-65 DEG C for 15-20 h, then take out the electrode and dry until dry.

5. A curved graphene based solid state lead acid battery as claimed in claim 1, wherein: The positive plate comprises the following components in mass ratio: 1000 parts of Pb powder, 10-100 parts of curved surface graphene powder, 1-5 parts of CMC sodium carboxymethyl cellulose, 0.1-1 parts of NANO SIO2(50 nm), 0.5-5 parts of NaSO4, 0.5-5 parts of CoSO4, 0.1-0.5 parts of PP fiber, 0.5-2 parts of H2SIF6 silicon fluoride acid, 70-80 parts of H2SO4 sulfuric acid, and 100-120 parts of deionized water.

6. A curved graphene based solid state lead-acid battery as claimed in claim 5, wherein: The particle size of the Pb lead powder is 250-300 mesh, the apparent density is 1.75-2 g / cm, the oxidation degree is 65-85%, and the water absorption is 110-140 g / kg; the particle size of the curved graphene powder is 6-9 Å, the electromotive force is 300-500 mv, the number of graphene sheets is 2-5, the sheet diameter is > 1 um, and the oxygen content on the surface of the graphene sheet structure is 35-60%; the particle size of NaSO4 and CoSO4 is 180 mesh; and the H2SO4 sulfuric acid is 25 DEG C d = 1.

40.

7. A curved graphene based solid state lead-acid battery as claimed in claim 6, wherein: The preparation process of the positive plate comprises the following steps: positive electrode paste: uniformly mix Pb lead powder, curved graphene powder, CMC sodium carboxymethyl cellulose, NANO SIO2 (50 nm), NaSO4, CoSO4, and PP fiber into mixed powder, uniformly mix H2SO4 sulfuric acid and deionized water, then pour them into a blender, add the mixed powder while stirring, after stirring for 10 min, add H2SO4 sulfuric acid with a specific gravity of 1.40 into the blender, stir for 45 min, adjust the deionized water according to the dry and wet conditions, and the apparent density of the lead paste is 340-355 g / cm; positive electrode coating: pad 2-3 layers of glass cloth on the coating workbench and place the grid, use a coating knife to coat the lead paste in the grid mesh, cover 1-2 layers of glass cloth after coating, repeatedly roll with a roller for 3-4 times, then turn the electrode over by 180 DEG, and coat the paste again in the same way as above; drying: place or hang the coated electrode in an oven, dry at 50-65 DEG C until the dryness degree is 50%; acid immersion: immerse in a sulfuric acid solution with a specific gravity of 25 DEG C D = 1.20 for 2-3 h, then take out and drip dry the acid solution, and dry in an oven at 50-65 DEG C until dry.

8. A curved graphene based solid state lead-acid battery as claimed in claim 1, wherein: The solid-state electrolyte comprises the following mass ratio components: 20-40 parts of curved graphene, 60-80 parts of fumed silica , 1-5 parts of lithium silicate , 1-10 parts of H2SO4 sulfuric acid.

9. A curved graphene based solid state lead-acid battery as claimed in claim 8, wherein: The particle size of the curved graphene is 6-9 Å, the electromotive force is 300-500 mv, the number of graphene sheets is 2-5, the sheet diameter is > 1 um, and the oxygen content on the surface of the graphene sheet structure is 35-60%; the H2SO4 sulfuric acid is 25 DEG C D = 1.14 ± 0.

005.

10. A curved graphene based solid state lead-acid battery as claimed in claim 9, wherein: The preparation process of the solid-state electrolyte comprises the following steps: The weighed fumed silica is added into the organic solvent and is subjected to ultrasonic dispersion treatment using an ultrasonic dispersion device for about 30-60 minutes, so that the fumed silica is uniformly dispersed in the organic solvent to form a uniform suspension. The weighed curved graphene is slowly added into the above suspension, and ultrasonic dispersion is continuously carried out for 60-120 min to ensure that the curved graphene is uniformly dispersed in the suspension The mixture is mixed evenly to form a mixed dispersion liquid; The weighed lithium silicate is added into the mixed dispersion liquid above, and stirring is performed using a high-speed stirring device, with the stirring speed controlled at 500-1000 r / min, and the stirring time being 60-120 min, so that the lithium silicate is uniformly dissolved and dispersed in the mixed system; In a stirring state, slowly drop H2SO4 sulfuric acid into the above-mentioned mixed system, control the dropping speed to be slow and uniform, observe the temperature and state changes of the system at the same time, keep stirring during the dropping process, continue stirring for 30-60 min after the dropping is completed, so that the sulfuric acid and other components fully react and mix; Transfer the above-mentioned mixed solution to a vacuum drying box, and perform vacuum drying treatment at a temperature of 60-80 DEG C until the organic solvent is completely volatilized and removed; Grind the dried solid mixture to make the particles smaller and more uniform, then according to the needs, use hot pressing or cold pressing to make the solid-state electrolyte into the required shape and size; Control the whole preparation process to be carried out in a dry and clean environment.

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