Super-hydrophobic interface modified lead carbon electrode, preparation method and electrolyte circulating system

Abstract

The invention provides a super-hydrophobic interface modified lead carbon electrode as well as a preparation method and an application system thereof. The electrode comprises a lead-carbon electrode substrate and a super-hydrophobic modification layer, the substrate is composed of lead powder, activated carbon, a conductive agent, a binder, carbon nanofibers and nano-silver particles according to a specific ratio, and the super-hydrophobic modification layer comprises a nano-hybrid modifier and a micron-sized structure enhancer. The preparation method of the electrode comprises the steps of substrate pretreatment, micron-sized array preparation, modification liquid preparation, coating and curing and the like. The invention further provides a matched self-adaptive electrolyte circulating system, and real-time monitoring and feedback control are achieved through pressure, temperature and concentration sensors. The problems that an existing lead carbon electrode is poor in interface wettability, serious in hydrogen evolution side reaction, prone to being corroded and the like are effectively solved, the cycle life of a battery is remarkably prolonged, and the rate capability and stability of the battery are remarkably improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrochemical energy storage and conversion, and specifically relates to a super-hydrophobic interface modified lead-carbon electrode, a preparation method thereof, and an adaptive electrolyte circulation system, which is particularly suitable for electrode material modification of secondary batteries such as lead-acid batteries and lithium-ion batteries. Background Art

[0002] The development of energy storage technology is crucial in today's energy sector. Lead-carbon batteries, with their low cost, high safety, and suitability for large-scale energy storage, have secured a significant position in the energy storage market. They are widely used in power system peak regulation and renewable energy grid-connected storage, among other applications. As the core component of lead-carbon batteries, the performance of lead-carbon electrodes directly determines the overall performance of the battery.

[0003] Currently, common materials used in lead-carbon electrode interface modification technologies primarily consist of common polymer coatings or simple inorganic films. While these materials can provide some degree of electrode protection, they exhibit poor hydrophobicity. Generally speaking, the interface contact angles formed by these common materials are mostly between 90° and 120°, failing to meet the standard of superhydrophobicity (contact angles greater than 150°). Furthermore, their stability is unsatisfactory. During long-term battery charge-discharge cycles, these modified layers are prone to detachment and decomposition due to factors such as electrolyte corrosion and temperature fluctuations. Traditional designs for electrolyte circulation systems typically employ a fixed-flow system. This system typically consists of a simple pump, piping, and a storage container. Throughout the battery's operation, the electrolyte circulates at a constant flow rate, regardless of the electrode's actual operating state. For example, in some early lead-carbon battery applications, a mechanical fixed-flow pump was used to drive the electrolyte circulation. The flow rate was typically set to a fixed value and did not adjust based on the battery's internal conditions.

[0004] Due to the deficiencies in hydrophobicity and stability of existing lead-carbon electrode modification materials, the interfacial compatibility between the electrode and the electrolyte is poor. This can cause a series of problems, such as the inability of the electrolyte to be evenly distributed on the electrode surface, resulting in inconsistent reaction activity in various parts of the electrode, which in turn affects the overall conductivity of the battery. At the same time, poor interfacial compatibility will also intensify the hydrogen and oxygen evolution reactions on the electrode surface, which not only consumes the water in the electrolyte and reduces the concentration of the electrolyte, but also produces gas on the electrode surface, hindering the conduction of electrons and seriously affecting the cycle life of the electrode. According to relevant research data, the lead-carbon electrode using traditional interface modification materials will show a significant decline in electrode performance after 500-800 charge and discharge cycles.

[0005] However, the traditional fixed-flow electrolyte circulation system cannot be adaptively adjusted according to the actual working state of the electrode and the consumption and pollution of the electrolyte. In the later stage of battery charging, the gas evolution reaction on the electrode surface intensifies, and the consumption and pollution of the electrolyte accelerate. At this time, the fixed-flow circulation cannot promptly remove the gas and heat generated on the electrode surface, nor can it quickly replenish fresh electrolyte, resulting in local overheating inside the battery and uneven electrolyte concentration, which further affects the performance of the battery. When the battery is in a discharged state or static state, the fixed-flow circulation will cause energy waste, because the battery's demand for electrolyte circulation is actually low at this time. In summary, the existing lead-carbon electrode interface modification technology and electrolyte circulation system seriously restrict the further improvement of lead-carbon battery performance and are in urgent need of improvement. Summary of the Invention

[0006] The present invention aims to solve the following key technical problems: Improve the electrode / electrolyte interface performance, reduce the contact angle, improve the electrolyte wettability and interface mass transfer efficiency, thereby improving the battery's charge acceptance and rate performance.

[0007] Effectively inhibit hydrogen evolution reaction, reduce electrode corrosion rate, extend battery life, and improve battery stability and reliability.

[0008] Enhance the structural stability of the electrode by optimizing the micro-nanostructure design and composite materials, improve the mechanical stability and anti-sulfation ability of the electrode, reduce structural damage during the cycle process, and significantly extend the cycle life of the battery.

[0009] The intelligent electrolyte circulation system can monitor the electrode interface status in real time, and dynamically adjust the electrolyte circulation parameters according to the monitoring results to improve the overall performance of the battery.

[0010] Develop an electrode preparation method that is simple in preparation process, low in cost and compatible with existing lead-acid battery production processes to facilitate the large-scale promotion and application of new technologies.

[0011] To solve the above technical problems, the present invention provides a super-hydrophobic interface modified lead-carbon electrode, comprising a lead-carbon electrode substrate and a super-hydrophobic modification layer, characterized in that the lead-carbon electrode substrate is composed of the following substances: Lead powder: purity ≥99.9%, average particle size 5-8μm; Activated carbon: Ketjen Black EC-600JD, with a specific surface area of ​​≥1400m 2 / g; Conductive agent: acetylene black, the addition amount is 3% of the lead powder mass; Binder: polytetrafluoroethylene (PTFE), 5% by mass; Carbon nanofiber CNF: the addition amount is 3% of the lead powder mass; Silver nanoparticles AgNPs: the addition amount is 2% of the lead powder mass; The mass ratio is: lead powder: activated carbon: conductive agent: binder: carbon nanofiber: nanosilver particles = 80:10:3:2:3:2; The super-hydrophobic modification layer includes a nano-hybrid modifier, which is composed of the following substances: Fluorosilane modified graphene quantum dots FS-GQD: The raw materials are graphene oxide quantum dots, the graphene oxide quantum dots GQD-COOH particle size is 10-20nm, and the oxygen-containing group content is 25-30%; tridecafluorooctyltrimethoxysilane FAS-17, perfluorodecyltriethoxysilane PFDTES; Hyperbranched polysiloxane HPS: molecular weight 5000-8000Da, branching degree ≥0.85, molecular chain containing 30-50 trimethoxysilane groups; Polyaniline-silica core-shell nanoparticles PANI-SiO2NPs; Nano-titanium dioxide: Anatase and rutile nano-titanium dioxide are mixed in a ratio of 1:1, with a particle size of 20-30nm and a total mass fraction of 2%; Ethanolamine: volume fraction 1%.

[0012] Preferably, the lead powder is first etched with 5% dilute hydrochloric acid for 10 minutes and then plasma treated to form a micro-pit structure with a roughness of Ra=1.5-1.8μm; the activated carbon is pretreated with argon at 500°C for 2 hours to remove surface oxygen-containing groups; the binder is uniformly dispersed in the matrix using an emulsion spray method; the carbon nanofibers CNF are subjected to acid-treated mixed solution, refluxed at 80°C for 3 hours, rinsed with deionized water to neutrality, and vacuum dried at 60°C for 4 hours; the nanosilver particles AgNPs are surface-modified with sodium citrate.

[0013] Preferably, the polyaniline-silica core-shell nanoparticles PANI-SiO2NPs are prepared by an in situ polymerization method, wherein nano-silica is dispersed in an aniline monomer solution, an initiator ammonium persulfate is added, and the polymerization reaction is carried out under acidic conditions for 6 hours to form PANI-SiO2NPs with a particle size of 50-80nm; the nano-titanium dioxide is dispersed in the modifying liquid to form photocatalytic self-cleaning sites on the electrode surface.

[0014] Preferably, the super-hydrophobic modification layer also includes a micron-scale structure enhancer PbO2-WO3 composite microrod: by adding different concentrations of sodium tungstate Na2WO4 to 0.5MH2SO4 electrolyte, a PbO2-WO3 composite microrod array with a diameter of 2-5μm and a length of 10-15μm is prepared on the surface of the lead substrate by a constant potential oxidation method, with a rod spacing of 5-8μm, forming a regular boss structure.

[0015] The present invention also provides a method for preparing a super-hydrophobic interface modified lead-carbon electrode, comprising the following steps: Step 1: Pretreatment of the lead-carbon electrode matrix, activation of the lead powder surface, modification of the activated carbon, and matrix pressing to obtain the electrode matrix; Step 2: Preparation of micron-sized PbO2-WO3 composite microrod arrays; Step 3: Preparation of superhydrophobic modification solution, including synthesis of fluorosilane-modified graphene quantum dots (FS-GQDs) and preparation of polyaniline-silica core-shell nanoparticles (PANI-SiO2NPs). Hybrid solution preparation; Step 4: coating and curing of the finishing layer, using an electrostatic spraying method, the finishing liquid is loaded into an electrostatic spray gun for spraying; and then curing is performed in steps.

[0016] Preferably, the step 1 includes the following steps: Step 11: Surface activation of lead powder: Add 5% dilute hydrochloric acid to the lead powder and ultrasonicate it for 15 minutes to remove the surface oxide film and form micron-sized pits. Then, rinse with deionized water until neutral, dry in a vacuum at 60°C for 4 hours, and then place the dried lead powder in a plasma treatment device and treat it at a power of 100 W for 15 minutes under an argon atmosphere. Step 12: Activated carbon modification: Place the activated carbon in a tube furnace and treat it at 500°C for 2 hours under an argon atmosphere. After cooling, pass it through a 200-mesh sieve to remove particle agglomerates. Step 13: Matrix pressing: Lead powder, activated carbon, conductive agent, PTFE emulsion, carbon nanofibers and nanosilver particles are mixed according to the ratio, first stirred at 500 rpm in a high-speed stirrer for 15 minutes, and then ultrasonically treated with an ultrasonic power of 200 W and an ultrasonic time of 15 minutes to form a uniform slurry; the slurry is coated on a lead foil current collector with a coating thickness of 300 μm, and the electrode matrix is ​​obtained by cold pressing at a pressure of 15 MPa and drying at 80°C for 12 hours.

[0017] The preparation method of the micron-sized PbO2-WO3 composite microrod array in step 2 is as follows: the pretreated electrode substrate is used as the working electrode, the platinum sheet is used as the counter electrode, and the saturated calomel electrode is used as the reference electrode. The electrodes are placed in a 0.5MH2SO4 electrolyte containing 0.05M Na2WO4, and oxidized at 1.8V for 20 minutes using a constant potential method to generate PbO2-WO3 composite microrods perpendicular to the substrate surface with a rod density of about 1×10 6 root / cm 2 .

[0018] The step 3 further comprises: Step 31: Synthesis of FS-GQDs: Add 200 mL of ethanol / water to a three-necked flask, add 2 g of GQD-COOH, and ultrasonically disperse for 30 min. Then, add 1.6 g of FAS-17 and 1.6 g of PFDTES according to the ratio, place in a microwave reactor, set the temperature to 60°C, and react for 30 min. After the reaction, centrifuge, collect the precipitate, and vacuum dry to obtain FS-GQD powder. Step 32: Preparation of PANI-SiO2NPs: In a reaction vessel, disperse 1 g of nano-silica in a solution containing 5 mL of aniline monomer, add 0.5 g of ammonium persulfate as an initiator, and adjust the solution pH to 2-3. Stir the reaction at room temperature for 6 h. After the reaction, centrifuge and collect the precipitate, wash it repeatedly with deionized water and ethanol, and dry it in a vacuum at 60°C for 12 h to obtain PANI-SiO2NPs. Step 33: Preparation of hybrid solution: Dissolve 5g of HPS in 200mL of toluene, add 10g of FS-GQDs, 10g of PANI-SiO2 NPs, 0.4g of mixed nano-titanium dioxide, and 2mL of ethanolamine. Ultrasonicate and disperse the mixture for 2h. Then, transfer the mixture to a ball mill and mill at 300rpm for 2h to form a homogeneous modified solution with an 8% solids content. Allow the solution to stand for 30min for degassing. The step 4 comprises: Step 41: Electrostatic Spraying: Using the electrostatic spraying method, place the finishing liquid into an electrostatic spray gun, apply a voltage of -50kV to the electrode surface, and spray at a pressure of 0.2MPa. Maintain a distance of 15-20cm between the nozzle and the electrode surface, and control the coating thickness to 5-8μm. After a single spraying, pre-dry at 60°C for 10 minutes. Repeat three times until a continuous film is formed. Step 42: Step-by-step curing: The coated electrode is first placed in an 80°C oven for pre-curing for 1 hour to initially cross-link the silicon-oxygen bonds between HPS molecules and between HPS and FS-GQDs; then the temperature is raised to 120°C for curing for 2 hours to further promote the cross-linking reaction and allow the HPS trimethoxy groups to fully react with the hydroxyl groups on the PbO2-WO3 surface to form covalent bonds.

[0019] The present invention also provides an adaptive electrolyte circulation system for the above-mentioned super-hydrophobic interface modified lead-carbon electrode, comprising: a pressure sensor; the pressure sensor is installed inside the battery near the electrode position, with an interval distance of less than 1-2 mm; the temperature sensor is arranged close to the PbO2-WO3 composite microrod array; 3-5 temperature sensors are evenly arranged on each square centimeter of electrode area; the concentration sensor is arranged close to the PbO2-WO3 composite microrod array, and 2-3 concentration sensors are arranged on each square centimeter of electrode area.

[0020] Preferably, it also includes a control system, which compares the pressure data with a preset pressure threshold range after receiving the digital signal fed back by the pressure sensor; and performs a comprehensive analysis based on the temperature data fed back by the temperature sensor and the concentration data fed back by the concentration sensor.

[0021] The present invention has the following significant technical effects: Excellent interfacial performance: The superhydrophobic modification layer significantly reduces the contact angle of the electrode / electrolyte interface, improves the wettability of the electrolyte, and increases the interfacial mass transfer efficiency, thereby significantly improving the battery's charge acceptance and rate performance.

[0022] Efficient hydrogen evolution inhibition: The synergistic effect of fluorosilane-modified graphene quantum dots and PbO2-WO3 composite microrods effectively inhibits the hydrogen evolution reaction, reduces the electrode corrosion rate, and extends the battery life.

[0023] Enhanced structural stability: Micro-nanostructure design and composite material optimization improve the mechanical stability and anti-sulfation ability of the electrode, reduce structural damage during the cycle process, and significantly extend the cycle life of the battery.

[0024] Intelligent adaptive regulation: The electrolyte circulation system with integrated sensors and feedback control system can monitor the electrode interface status in real time and dynamically adjust the electrolyte circulation parameters, realizing intelligent operation of the battery and improving the overall performance.

[0025] Good compatibility: The electrode preparation process of the present invention is simple, low-cost, compatible with the existing lead-acid battery production process, and easy to promote and apply on a large scale. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The present invention provides a flow chart of a method for preparing a super-hydrophobic interface modified lead-carbon electrode.

[0027] Figure 2 This is a logic diagram of the adaptive electrolyte circulation system provided by the present invention. DETAILED DESCRIPTION

[0028] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0029] The following will be combined with the accompanying drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments.

[0030] In a first embodiment of the present invention, a super-hydrophobic interface-modified lead-carbon electrode is provided, comprising a lead-carbon electrode substrate and a super-hydrophobic modification layer.

[0031] The lead-carbon electrode matrix components are: Lead powder: purity ≥99.9%, average particle size 5-8μm, first etched with 5% dilute hydrochloric acid for 10 minutes, then plasma treated (under argon atmosphere, 100W power treatment for 15 minutes) to form a micro-pit structure with a roughness of Ra=1.5-1.8μm, enhancing the mechanical bite with the modified layer.

[0032] Activated carbon: Ketjen Black EC-600JD, with a specific surface area of ​​≥1400m 2 / g, and was pretreated with argon at 500℃ for 2h to remove surface oxygen groups and improve the electron conduction efficiency.

[0033] Conductive agent: acetylene black, added in an amount of 3% of the lead powder mass, is used to build a conductive network between activated carbon and the lead matrix.

[0034] Binder: Polytetrafluoroethylene (PTFE), mass fraction 5%, is evenly dispersed in the matrix by emulsion spray method to enhance the stability of the electrode structure.

[0035] Carbon nanofiber (CNF): After acid treatment (immersion in a mixed solution of concentrated nitric acid and concentrated sulfuric acid (volume ratio 1:3), reflux reaction at 80℃ for 3 hours, rinsed with deionized water until neutral, and vacuum dried at 60℃ for 4 hours), the addition amount is 3% of the mass of lead powder to enhance the conductive network.

[0036] Silver nanoparticles (AgNPs): Surface modified with sodium citrate (add an appropriate amount of sodium citrate to the silver nanoparticle solution and stir for 2 hours), with the addition amount being 2% of the lead powder mass, to accelerate the electrode reaction kinetics.

[0037] Ratio: lead powder: activated carbon: conductive agent: binder: carbon nanofiber: nanosilver particles = 80:10:3:2:3:2 (mass ratio).

[0038] The super-hydrophobic modification layer includes a nano-hybrid modifier, which is composed of the following substances: Fluorosilane-modified graphene quantum dots (FS-GQD): Raw materials: graphene oxide quantum dots (GQD-COOH, particle size 10-20 nm, oxygen group content 25-30%), tridecafluorooctyltrimethoxysilane (FAS-17), and perfluorodecyltriethoxysilane (PFDTES). Modification method: Using microwave-assisted synthesis, GQD-COOH was dispersed in ethanol / water (volume ratio 3:1) to a concentration of 10 mg / mL. FAS-17 and PFDTES were then added (total mass ratio of GQD to FAS-17 and PFDTES was 1:1.6, FAS-17:PFDTES = 1:1). The mixture was placed in a microwave reactor and reacted at 60°C for 30 min. Through the hydrolysis-condensation reaction of the silane coupling agent, long chains of -CF2(CF2)6CH3 and -CF2(CF2)8CH3 were grafted onto the GQD surface, forming a hydrophobic conductive core.

[0039] Hyperbranched polysiloxane (HPS): molecular weight 5000-8000Da, branching degree ≥0.85, molecular chain containing 30-50 trimethoxysilane groups, which acts as a crosslinker to react with FS-GQD and lead matrix surface hydroxyl groups to form a three-dimensional network structure.

[0040] Polyaniline-silica core-shell nanoparticles (PANI-SiO2NPs): Prepared by in situ polymerization, nano-silica is dispersed in an aniline monomer solution, and the initiator ammonium persulfate is added. The polymerization reaction is carried out under acidic conditions (pH = 2-3) for 6 hours to form PANI-SiO2NPs with a particle size of 50-80nm. The addition amount is 5% of the mass of the modification solution to enhance the conductive and mechanical properties of the modification layer.

[0041] Nano-titanium dioxide: Anatase and rutile nano-titanium dioxide are mixed in a 1:1 ratio (particle size 20-30nm), with a total mass fraction of 2%, and dispersed in the modification solution to form photocatalytic self-cleaning sites on the electrode surface to decompose adsorbed organic impurities.

[0042] Ethanolamine: 1% by volume, acts as a catalyst to promote the hydrolysis and condensation reaction of silane groups.

[0043] The superhydrophobic modification layer also includes a micron-scale structural enhancer, including PbO2-WO3 composite microrods: by adding different concentrations (such as 0.05M) of sodium tungstate (Na2WO4) to a 0.5MH2SO4 electrolyte, a constant potential oxidation method (1.8V vs. SCE, 20min) is used to prepare a PbO2-WO3 composite microrod array with a diameter of 2-5μm and a length of 10-15μm on the surface of a lead substrate. The rod spacing is 5-8μm, forming a regular boss structure to provide anchor points for the modification layer.

[0044] like Figure 1As shown, in another embodiment of the present invention, a method for preparing a super-hydrophobic interface modified lead-carbon electrode is provided, comprising the following steps: Step 1: Pretreatment of the lead-carbon electrode substrate, including the following steps: Step 11: Surface Activation of Lead Powder: The lead powder was added to 5% dilute hydrochloric acid (liquid-to-solid ratio 5:1) and ultrasonically treated for 15 minutes to remove the surface oxide film and form micron-sized pits. The powder was then rinsed with deionized water until neutral and dried under vacuum at 60°C for 4 hours. The dried lead powder was then placed in a plasma treatment apparatus and treated at 100 W for 15 minutes under an argon atmosphere.

[0045] Step 12: Modification of activated carbon: Place the activated carbon in a tubular furnace and treat it at 500°C for 2 hours under an argon atmosphere. After cooling, pass it through a 200-mesh sieve to remove particle agglomerates.

[0046] Step 13: Matrix Pressing: Mix lead powder, activated carbon, conductive agent, PTFE emulsion, carbon nanofibers, and silver nanoparticles according to the appropriate ratio. Stir in a high-speed blender at 500 rpm for 15 minutes, then ultrasonicate at 200 W for 15 minutes to form a uniform slurry. Apply the slurry to a lead foil current collector (0.1 mm thick) to a coating thickness of 300 μm. Cold press at 15 MPa pressure and dry at 80°C for 12 hours to produce the electrode matrix.

[0047] Step 2: Preparation of micron-sized PbO2-WO3 composite microrod arrays. The method is as follows: The pretreated electrode substrate is used as the working electrode, the platinum sheet is used as the counter electrode, and the saturated calomel electrode is used as the reference electrode. The electrodes are placed in an electrolyte containing 0.05M Na2WO4 in 0.5MH2SO4. The electrodes are oxidized at 1.8V for 20 minutes using a constant potential method to generate PbO2-WO3 composite microrods perpendicular to the substrate surface. The rod density is approximately 1×10 6 root / cm 2 The growth process of the composite microrods was observed in real time using a scanning electron microscope (SEM), and the oxidation time and potential were fine-tuned according to the growth situation to ensure that the morphology and size of the composite microrods met expectations.

[0048] Step 3, preparation of super-hydrophobic modification liquid, specific method: Step 31: Synthesis of FS-GQDs: Add 200 mL of ethanol / water (3:1) to a three-necked flask, add 2 g of GQD-COOH, and ultrasonically disperse for 30 min. Add 1.6 g of FAS-17 and 1.6 g of PFDTES according to the ratio. Place the mixture in a microwave reactor at 60°C and react for 30 min. After the reaction, centrifuge at 8000 rpm for 10 min, collect the precipitate, and vacuum dry to obtain FS-GQD powder.

[0049] Step 32: Preparation of PANI-SiO2 NPs: In a reaction vessel, disperse 1 g of nanosilica in a solution containing 5 mL of aniline monomer. Add 0.5 g of ammonium persulfate as an initiator, and adjust the solution pH to 2-3. Stir the reaction at room temperature for 6 h. After the reaction, centrifuge (6000 rpm, 15 min). Collect the precipitate, wash it repeatedly with deionized water and ethanol, and dry it in a vacuum at 60°C for 12 h to obtain PANI-SiO2 NPs.

[0050] Step 33: Preparation of hybrid solution: Dissolve 5g of HPS in 200mL of toluene, add 10g of FS-GQDs, 10g of PANI-SiO2 NPs, 0.4g of mixed nano-titanium dioxide, and 2mL of ethanolamine. Ultrasonicate and disperse the mixture for 2h. Then, transfer the mixture to a ball mill and mill at 300rpm for 2h to form a homogeneous modified solution with an 8% solids content. Allow the solution to stand for 30min for degassing.

[0051] Step 4: Apply and cure the finishing layer. The specific method is as follows: Step 41: Electrostatic Spraying: Using the electrostatic spraying method, the finishing liquid is loaded into an electrostatic spray gun. A voltage of -50 kV is applied to the electrode surface, and the spray is applied at a pressure of 0.2 MPa. The distance between the nozzle and the electrode surface is controlled at 15-20 cm, and the coating thickness is controlled to 5-8 μm. After a single spraying, pre-dry at 60°C for 10 minutes. Repeat three times until a continuous film is formed. During the spraying process, the coating uniformity is monitored in real time, and the spray gun movement speed and angle are adjusted to ensure that the finishing liquid evenly covers the electrode surface.

[0052] Step 42: Step-by-step curing: The coated electrode was pre-cured in an 80°C oven for 1 hour to initiate crosslinking between the HPS molecules and between the HPS and FS-GQDs. The temperature was then raised to 120°C for 2 hours to further promote the crosslinking reaction and allow the HPS trimethoxy groups to fully react with the hydroxyl groups on the PbO2-WO3 surface, forming covalent bonds (Si-O-Pb and Si-O-W bonds), enhancing interfacial bonding. During the curing process, Fourier transform infrared spectroscopy (FT-IR) was used to monitor the formation of chemical bonds in real time to ensure the curing reaction was fully progressing.

[0053] The structural characterization of the obtained super-hydrophobic interface modified lead-carbon electrode product is as follows: Macrostructure: Observe the color, texture, and coating integrity of the modified electrode surface, and record the coating thickness. Repeatedly bend the electrode (180° for 100 cycles) to observe whether the coating will detach. Use a tensile testing machine to test the adhesion of the coating to the substrate and accurately measure the coating's flexibility and adhesion strength. Also, use a surface profilometer to measure the macroscopic roughness of the electrode surface. Compare this to an unmodified electrode to analyze the effect of the modified layer on the electrode's macroscopic surface morphology.

[0054] Microstructure: SEM Observation: The electrode surface microstructure was observed using a scanning electron microscope (SEM) at different magnifications. The array distribution of the PbO2-WO3 composite microrods was observed at low magnification (500×), and the rod diameter, length, spacing, and density were calculated to analyze their uniformity. The dispersion of FS-GQDs and PANI-SiO2 NPs in the HPS matrix was observed at high magnification (20,000×), measuring the size and distribution density of hydrophobic clusters, as well as the size and distribution of nanoscale gaps between clusters. SEM-EDS (energy dispersive X-ray spectroscopy) was used to analyze the elemental composition of different regions and determine the distribution of each component.

[0055] TEM Analysis: The microstructure of FS-GQDs and PANI-SiO2NPs was analyzed using transmission electron microscopy. The morphology of the fluorocarbon chains on the FS-GQD surface was observed, confirming the successful grafting of FAS-17 and PFDTES. The core-shell structure of the PANI-SiO2NPs was analyzed, and the shell thickness was measured. Selected area electron diffraction (SAED) was used to analyze the crystal structure of FS-GQDs and PANI-SiO2NPs and study their crystalline properties.

[0056] XPS detection: X-ray photoelectron spectrometer is used to analyze the elements on the surface of the modified layer. Accurately measure the CF bond, Si-O-Si bond, Pb element (including Pb 2+ and Pb 0 ) and the content and chemical state of W (from PbO2-WO3). Peak fitting is used to deeply analyze the existence of each element in different chemical environments and reveal the chemical bonding mode between the modified layer and the substrate.

[0057] AFM analysis: Atomic force microscopy (AFM) is used to measure the nanoscale roughness of the modified layer surface, obtaining a three-dimensional image of the surface topography. The distribution of nanoscale hydrophobic clusters and conductive channels is analyzed, and their height, width, and other parameters are measured, providing a deep understanding of the surface structure of the modified layer at the nanoscale.

[0058] Raman spectroscopy: The modified layer was analyzed using a Raman spectrometer. The position and intensity of characteristic peaks confirmed the grafting of FAS-17 and PFDTES, as well as the structural characteristics of polyaniline and silica in the PANI-SiO2 NPs. The vibrational modes of the chemical bonds in the modified layer were studied, providing further evidence for its structure and properties.

[0059] Contact Angle Measurement: A contact angle meter was used to measure the contact angle and sliding angle of deionized water and 1M H₂SO₄ on the modified electrode surface. Measurements were taken at regular intervals (e.g., 10 charge-discharge cycles), and the change in contact angle over time or cycle number was recorded to assess the hydrophobic durability and resistance to electrolyte corrosion of the modified layer. Contact angles were also measured at different temperatures to investigate the effect of temperature on the hydrophobic properties of the modified layer.

[0060] Lead-carbon electrodes modified with a superhydrophobic interface demonstrate significant advantages in improving battery performance. To further optimize overall battery performance, the present invention also provides a closely associated adaptive electrolyte circulation system. This system intelligently adjusts electrolyte circulation parameters based on the needs of the lead-carbon electrode under different operating conditions, thereby improving battery stability, charge-discharge efficiency, and service life.

[0061] like Figure 2 As shown, the present invention also provides an adaptive electrolyte circulation system, comprising: Electrolyte storage tanks: Made of high-strength, corrosion-resistant engineering plastics, they offer a large capacity to meet the battery's electrolyte requirements during different operating stages. A liquid level sensor within the tank monitors the electrolyte level in real time and transmits the signal to the control system. Furthermore, the tanks are equipped with heating and cooling devices, which precisely control the electrolyte temperature using feedback from built-in temperature sensors to ensure the electrolyte remains within the optimal operating temperature range.

[0062] Circulation Pump: A high-precision, low-energy magnetic drive pump is used to precisely control the electrolyte flow rate. This pump offers excellent sealing properties, effectively preventing electrolyte leakage. The pump speed is adjusted by the control system based on the battery's real-time operating conditions, enabling precise control of the electrolyte circulation rate.

[0063] Flow Control Valve: Installed on the circulation pipeline, it receives signals from the control system to precisely adjust the electrolyte flow rate. Using electric or pneumatic actuators, the control valve offers fast response and high-precision regulation, allowing it to flexibly distribute electrolyte flow according to the needs of different battery locations.

[0064] Temperature sensors: Temperature sensors are installed at key locations within the battery and on the electrolyte circulation piping to monitor the temperature of the electrolyte and electrodes in real time. These sensors provide real-time feedback to the control system, enabling the system to adjust electrolyte temperature and circulation parameters.

[0065] Concentration sensors: These sensors are installed in the electrolyte storage tank and circulation piping to monitor the concentration of key components in the electrolyte, such as sulfuric acid, in real time. Using advanced electrochemical sensing technology, these sensors can quickly and accurately detect concentration changes and transmit the data to the control system.

[0066] Control system: As the core of the entire adaptive electrolyte circulation system, it utilizes a high-performance microprocessor and advanced control algorithms. It receives real-time data from level sensors, temperature sensors, and concentration sensors. Through complex logic operations and data analysis, it precisely controls the speed of the circulation pump, the opening of the flow control valve, and the heating and cooling devices of the electrolyte storage tank, achieving adaptive regulation of the electrolyte circulation system.

[0067] The electrolyte storage tank's inlet is connected via a pipe to an external electrolyte replenishment device (such as a refill tank) for replenishing electrolyte when the liquid level is too low. The tank's outlet is connected to the suction port of a circulation pump, which delivers the electrolyte in the tank to the circulation pump, providing power for the entire circulation system.

[0068] The return port of the electrolyte storage tank is connected to the circulation pipeline to receive the electrolyte reflux after the battery reaction, so that the electrolyte can be recycled.

[0069] The electrolyte storage tank's temperature control interface is connected to a heating and cooling device to regulate the electrolyte temperature within the tank. The heating and cooling device is connected to an external heating source (such as a hot water circulation system) or cooling source (such as a chiller) via a pipe.

[0070] The sensor interface of the electrolyte storage tank is connected to a liquid level sensor and a temperature sensor, and is used to monitor the liquid level and temperature information of the electrolyte in the storage tank in real time.

[0071] The suction port of the circulation pump is connected to the liquid outlet of the electrolyte storage tank to absorb the electrolyte in the storage tank.

[0072] The discharge port of the circulation pump is connected to the inlet of the flow regulating valve through a pipeline, so as to transport the pressurized electrolyte to the flow regulating valve.

[0073] The circulating pump draws in liquid from the electrolyte storage tank as the conveying medium.

[0074] The circulation pump receives a speed regulation signal from the control system and adjusts the speed of the pump according to the battery operating conditions, thereby controlling the electrolyte flow rate.

[0075] The inlet of the flow regulating valve is connected to the outlet of the circulation pump to receive the electrolyte delivered by the circulation pump.

[0076] The outlet of the flow control valve is connected to the electrolyte inlet of the battery through a pipe, transporting the flow-regulated electrolyte into the battery. At the same time, inside the battery, the electrolyte circulates through the channels around the electrodes to react.

[0077] The flow regulating valve receives an opening adjustment signal from the control system according to the battery operating conditions (such as temperature, concentration, etc.) to accurately control the electrolyte flow.

[0078] The electrolyte of the flow regulating valve is output to the battery to provide an appropriate amount of electrolyte for the electrode reaction in the battery and ensure that the electrolyte is reasonably distributed around the electrode.

[0079] The temperature sensor measuring ends are distributed in multiple key locations inside the battery (such as near the electrodes, electrolyte flow channels, etc.) and on the electrolyte circulation pipeline, directly contacting the measured medium (electrolyte or electrode surface) to sense temperature changes in real time.

[0080] The signal output end of the temperature sensor is connected to the data acquisition module of the control system through a signal line to transmit the measured temperature data to the control system.

[0081] The temperature sensor receives heat from the surrounding environment (electrolyte or electrode) through heat conduction or heat convection, causing changes in its own electrical characteristics (such as resistance, voltage, etc.), thereby sensing temperature.

[0082] The temperature sensor outputs an electrical signal corresponding to the temperature (such as a voltage signal, a resistance signal, etc.) to the control system, which is converted into a digital signal by the data acquisition module and then analyzed and processed by the control system, serving as an important basis for adjusting the electrolyte temperature and circulation parameters.

[0083] The measuring end of the concentration sensor is installed on the electrolyte storage tank and the circulation pipeline, is in direct contact with the electrolyte, and is used to monitor the concentration of key components such as sulfuric acid in the electrolyte in real time.

[0084] The signal output end of the concentration sensor is connected to the data acquisition module of the control system through a signal line to transmit the detected concentration data to the control system.

[0085] The concentration sensor outputs an electrical signal corresponding to the electrolyte concentration to the control system, which is converted into a digital signal by the data acquisition module for the control system to calculate and decide whether the electrolyte concentration needs to be adjusted and how to adjust it.

[0086] The data acquisition end of the control system is connected to the signal output ends of the temperature sensor, concentration sensor and liquid level sensor through signal lines, so as to obtain data such as the internal temperature of the battery, the concentration of the electrolyte and the liquid level of the storage tank in real time.

[0087] The control output end of the control system is connected to the circulation pump, flow regulating valve and heating and cooling devices of the electrolyte storage tank through control lines, and sends control instructions to these devices based on the collected data and preset algorithms.

[0088] The input data of the control system includes: Temperature data: Obtain real-time temperature information of various parts of the battery and the electrolyte from the temperature sensor.

[0089] Concentration data: Obtain real-time concentration data of key components in the electrolyte from the concentration sensor.

[0090] Liquid level data: Get the liquid level height information in the electrolyte storage tank from the liquid level sensor.

[0091] The outputs of the control system include: Pump control signal: Sends speed adjustment signal to the circulation pump to control the electrolyte circulation flow.

[0092] Valve control signal: Sends opening adjustment signal to the flow control valve to accurately adjust the electrolyte flow distribution.

[0093] Temperature adjustment signal: Sends control signals to the heating and cooling devices of the electrolyte storage tank to adjust the electrolyte temperature.

[0094] The system works as follows: Adaptive temperature regulation: When the temperature sensor detects that the temperature inside the battery or on the electrode surface is too high, the control system issues a command to increase the speed of the circulation pump, increasing the electrolyte circulation flow rate, accelerating heat transfer, and allowing the electrolyte to more quickly remove heat generated by the electrode; it also activates the cooling device of the electrolyte storage tank to reduce the electrolyte temperature. Conversely, if the temperature is too low, the control system reduces the speed of the circulation pump, reducing the electrolyte flow rate, and activates the heating device to increase the electrolyte temperature, ensuring that the electrode always operates within the appropriate temperature range and fully utilizing the performance advantages of the superhydrophobic interface modified lead-carbon electrode.

[0095] Adaptive Concentration Adjustment: A concentration sensor monitors the concentration of sulfuric acid and other components in the electrolyte in real time. The electrolyte concentration fluctuates during the battery's charge and discharge processes. When the concentration sensor detects a deviation from the optimal range, the control system calculates the amount of electrolyte required for replenishment or dilution based on the deviation. By controlling the flow control valve, the control system adds an appropriate amount of concentrated electrolyte or distilled water to the circulation system to maintain a stable electrolyte concentration. This helps maintain a favorable chemical reaction between the electrodes and the electrolyte, improving the battery's charge and discharge efficiency and stability.

[0096] Adaptive Liquid Level Adjustment: A liquid level sensor monitors the liquid level in the electrolyte storage tank in real time. When the liquid level is too low, the control system issues an alarm and automatically activates the refill device to replenish the electrolyte in the tank. If the liquid level is too high, the control system controls the relevant valves to drain or recycle the excess electrolyte, ensuring that the liquid level in the electrolyte storage tank remains within a safe and appropriate range, ensuring the normal operation of the circulation system.

[0097] Preferably, the adaptive electrolyte circulation system also includes a pressure sensor. The pressure sensor is installed inside the battery near the electrode position: inside the battery, the pressure sensor is precisely arranged in an area very close to the surface of the super-hydrophobic interface modified lead-carbon electrode. Ideally, the spacing distance is controlled within 1-2 mm. This is because the electrolyte pressure near the electrode surface directly affects the interaction between the electrolyte and the electrode, especially for the super-hydrophobic interface modified lead-carbon electrode, whose unique dual-scale structure (micrometer-scale PbO2-WO3 composite microrod array and nano-scale hydrophobic cluster) is easily affected by pressure changes. Multiple pressure sensors are reasonably distributed around and in the center of the lead-carbon electrode to ensure that the pressure conditions near different parts of the electrode can be fully monitored. For example, for larger electrodes, a pressure sensor can be installed at each of the four corners and the center of the electrode to obtain detailed information on the pressure distribution on the electrode surface.

[0098] Furthermore, on the electrolyte circulation pipeline, pressure sensors are installed at several key nodes. First, a pressure sensor is installed at the outlet of the circulation pump to monitor the initial pressure of the electrolyte after being pressurized by the pump. This helps to understand the working status of the circulation pump and whether the output pressure meets the system design requirements. Secondly, pressure sensors are installed before and after the flow control valve. By comparing the pressure data at these two positions, the regulating effect of the flow control valve on the electrolyte pressure can be accurately evaluated, and it can be judged whether the valve is working properly and the impact of the opening change on the pressure. In addition, pressure sensors are also installed at the inlet of the electrolyte entering the battery and the outlet of the battery to monitor the pressure changes of the electrolyte when entering and leaving the battery, and provide the control system with key information such as the internal pressure loss of the battery.

[0099] High-precision piezoresistive pressure sensors operate based on the piezoresistive effect. When pressure is applied to the sensor's sensitive element, its resistance changes. By measuring this change in resistance, the applied pressure can be accurately calculated. These pressure sensors monitor the electrolyte pressure in real time and feed it back to the control system in the form of an electrical signal (such as voltage or current). The sensor's sampling frequency is set to 10-100Hz to ensure timely capture of instantaneous pressure changes. The data acquisition module in the control system converts the received analog electrical signal into a digital signal and performs preliminary filtering to remove noise interference, ensuring data accuracy and reliability.

[0100] After receiving the digital signal from the pressure sensor, the control system compares the pressure data with a pre-set pressure threshold range. It also performs a comprehensive analysis based on the temperature data from the temperature sensor and the concentration data from the concentration sensor. For example, as the temperature increases, the viscosity of the electrolyte may decrease, causing the pressure to change at the same flow rate. Changes in concentration can also affect the physical properties of the electrolyte, which in turn affects the pressure. Using a complex algorithm model, the control system accurately calculates the required circulation pump speed and flow control valve opening to maintain the electrolyte flow rate and pressure consistent with the structural characteristics of the superhydrophobic interface-modified lead-carbon electrode based on these multiple parameters. If the pressure near the electrode surface is detected to be too high, potentially damaging the superhydrophobic coating, the control system reduces the circulation pump speed and appropriately increases the flow control valve opening to reduce the electrolyte flow rate and pressure. Conversely, if the pressure is too low, potentially affecting sufficient contact and reaction between the electrolyte and the electrode, the control system increases the circulation pump speed, decreases the flow control valve opening, and increases the pressure. Through this real-time and precise adjustment mechanism, the damage to the modified layer caused by uneven pressure can be effectively reduced, ensuring the stability of the electrode structure and the reliability of its performance.

[0101] More preferably, the temperature sensor is arranged near the PbO2-WO3 composite microrod array. The distribution of temperature sensors is encrypted near the PbO2-WO3 composite microrod array of the superhydrophobic interface modified lead-carbon electrode. Since the PbO2-WO3 composite microrod array is an important place for electrode reaction, the temperature change on its surface has a significant effect on the electrode reaction kinetics. 3-5 micro temperature sensors are evenly arranged on each square centimeter of electrode area. The size of these sensors should be as small as possible, for example, the diameter does not exceed 0.5mm, so as to avoid significant interference with the electrode structure and the flow of the electrolyte. The sensor adopts a thin film temperature sensor, which has the characteristics of fast response speed and high precision, and can quickly and accurately sense the temperature changes of the electrolyte near the microrod array.

[0102] More preferably, the number of temperature sensors is increased in areas where nanohybrid modifiers are concentrated (such as those formed by FS-GQDs and HPS). Nanohybrid modifiers are highly sensitive to temperature, and their performance and structural stability are closely related to temperature. In these areas, a density of 2-3 temperature sensors per 0.5 square centimeters is used. These temperature sensors are connected to the control system via flexible wires, ensuring that even minor electrode deformation during battery operation will not affect the normal operation of the sensors and data transmission.

[0103] More preferably, the concentration sensors are positioned close to the PbO2-WO3 composite microrod array: Highly sensitive concentration sensors are placed around the PbO2-WO3 composite microrod array. Because this area is critical for the chemical reaction between the electrolyte and the electrodes, the concentration of the ions involved in the reaction fluctuates rapidly and significantly impacts the reaction process. Using concentration sensors based on electrochemical principles, they can quickly and accurately detect the concentrations of key ions (such as sulfate and lead ions) in the electrolyte. Placing two to three concentration sensors per square centimeter of electrode area ensures real-time monitoring of subtle changes in electrolyte concentration in this area.

[0104] In areas where nanohybrid modifiers are concentrated, precise monitoring of electrolyte concentration is also necessary. The performance of nanohybrid modifiers can be affected by electrolyte concentration. For example, excessively high or low sulfuric acid concentrations can alter the modifier's surface properties and conductivity. In this area, concentration sensors are installed at a density of 1-2 per 0.5 square centimeters. A wireless data transmission module connects the concentration sensors to the control system, preventing excessive wires from obstructing the electrode structure and electrolyte flow while ensuring timely and stable data transmission to the control system.

[0105] By placing the temperature sensor and concentration sensor closer to the key reaction area of ​​the superhydrophobic interface modified lead-carbon electrode and increasing the sensor distribution density, the temperature and concentration changes of the electrolyte on the electrode surface can be monitored more accurately. After these precise data are transmitted to the control system, the control system can fine-tune the electrolyte circulation parameters based on real-time temperature and concentration information, combined with other parameters such as pressure. For example, when it is detected that the electrolyte temperature near the PbO2-WO3 composite microrod array increases and the concentration decreases, the control system can judge that the electrode reaction rate may accelerate and more electrolyte is needed to participate in the reaction. At this time, the control system will appropriately increase the speed of the circulation pump and adjust the opening of the flow control valve to allow more electrolyte to flow quickly to the area. According to the concentration data, the right amount of concentrate is accurately added to maintain the stability of the electrolyte concentration, thereby better meeting the electrode reaction requirements and improving the overall performance and stability of the battery.

[0106] The superhydrophobic interface-modified lead-carbon electrode exhibits excellent interfacial properties through unique dual-scale structural regulation and integrated conductive and hydrophobic modification. The adaptive electrolyte circulation system creates a more stable and suitable working environment for the electrode. For example, the system's precise control of electrolyte temperature and concentration helps maintain the stability of the superhydrophobic modification layer, preventing damage to the modification layer due to excessive temperature or abnormal electrolyte concentration, thereby further extending the service life of the electrode. At the same time, a stable working environment enables the electrode's dual-scale hydrophobic structure and conductive channels to function better, improving the electrode's charge and discharge performance.

[0107] The superhydrophobic interface-modified lead-carbon electrode, constructed from a micron-sized PbO2-WO3 composite microrod array and a nanohybrid modifier, provides abundant active sites for electrode reactions. The adaptive electrolyte circulation system ensures uniform electrolyte distribution around these active sites, replenishing the necessary ions and promoting the electrode reaction. Furthermore, the system's precise regulation of electrolyte parameters optimizes the double-layer properties at the electrode-electrolyte interface, reducing charge transfer resistance and improving the battery's energy conversion efficiency.

[0108] The superhydrophobic coating forms a strong bond with the electrode substrate through chemical anchoring and mechanical interlocking. The adaptive electrolyte circulation system maintains a stable electrolyte flow and appropriate parameters, reducing electrolyte erosion and corrosion on the electrode surface, further enhancing the stability of the bond between the coating and the electrode substrate. For example, stable electrolyte temperature and flow prevent the coating from shedding due to thermal stress or fluid impact, ensuring the integrity of the electrode structure during long-term use.

[0109] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be included therein. Any reference sign in a claim should not be construed as limiting the claim to which it relates.

[0110] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A super-hydrophobic interface modified lead-carbon electrode, comprising a lead-carbon electrode substrate and a super-hydrophobic modification layer, characterized in that: The lead-carbon electrode matrix is ​​composed of the following substances: Lead powder: purity ≥99.9%, average particle size 5-8μm; Activated carbon: Ketjen Black EC-600JD, with a specific surface area of ​​≥1400m² / g; Conductive agent: acetylene black, the addition amount is 3% of the lead powder mass; Binder: polytetrafluoroethylene (PTFE), 5% by mass; Carbon nanofiber CNF: the addition amount is 3% of the lead powder mass; Silver nanoparticles AgNPs: the addition amount is 2% of the lead powder mass; The mass ratio is: lead powder: activated carbon: conductive agent: binder: carbon nanofiber: nanosilver particles = 80:10:3:2:3:2; The super-hydrophobic modification layer includes a nano-hybrid modifier, which is composed of the following substances: Fluorosilane modified graphene quantum dots FS-GQD: The raw materials are graphene oxide quantum dots, the graphene oxide quantum dots GQD-COOH particle size is 10-20nm, and the oxygen-containing group content is 25-30%; tridecafluorooctyltrimethoxysilane FAS-17, perfluorodecyltriethoxysilane PFDTES; Hyperbranched polysiloxane HPS: molecular weight 5000-8000Da, branching degree ≥0.85, molecular chain containing 30-50 trimethoxysilane groups; Polyaniline-silica core-shell nanoparticles PANI-SiO2NPs; Nano-titanium dioxide: Anatase and rutile nano-titanium dioxide are mixed in a ratio of 1:1, with a particle size of 20-30nm and a total mass fraction of 2%; Ethanolamine: volume fraction 1%.

2. A super-hydrophobic interface modified lead-carbon electrode according to claim 1, characterized in that: The lead powder is first etched with 5% dilute hydrochloric acid for 10 minutes and then plasma treated to form a micro-pit structure with a roughness of Ra=1.5-1.8μm; the activated carbon is pretreated with argon at 500°C for 2 hours to remove surface oxygen-containing groups; the binder is uniformly dispersed in the matrix using an emulsion spray method; the carbon nanofibers (CNF) are subjected to an acid-treated mixed solution, refluxed at 80°C for 3 hours, rinsed with deionized water until neutral, and vacuum dried at 60°C for 4 hours; the silver nanoparticles (AgNPs) are surface-modified with sodium citrate.

3. A super-hydrophobic interface modified lead-carbon electrode according to claim 2, characterized in that: The polyaniline-silica core-shell nanoparticles PANI-SiO2NPs are prepared by an in-situ polymerization method. Nano-silica is dispersed in an aniline monomer solution, and an initiator, ammonium persulfate, is added. The polymerization reaction is carried out under acidic conditions for 6 hours to form PANI-SiO2NPs with a particle size of 50-80nm. The nano-titanium dioxide is dispersed in the modification solution to form photocatalytic self-cleaning sites on the electrode surface.

4. A super-hydrophobic interface modified lead-carbon electrode according to claim 3, characterized in that: The super-hydrophobic modification layer also includes a micron-scale structural enhancer, PbO2-WO3 composite microrods: by adding different concentrations of sodium tungstate Na2WO4 to a 0.5MH2SO4 electrolyte, a PbO2-WO3 composite microrod array with a diameter of 2-5 μm and a length of 10-15 μm is prepared on the surface of a lead substrate using a constant potential oxidation method. The rod spacing is 5-8 μm, forming a regular boss structure.

5. A method for preparing a super-hydrophobic interface modified lead-carbon electrode as claimed in claim 4, comprising the following steps: Step 1: Pretreatment of the lead-carbon electrode matrix, activation of the lead powder surface, modification of the activated carbon, and matrix pressing to obtain the electrode matrix; Step 2: Preparation of micron-sized PbO2-WO3 composite microrod arrays; Step 3, preparation of superhydrophobic modification solution, including synthesis of fluorosilane-modified graphene quantum dots FS-GQD and preparation of polyaniline-silica core-shell nanoparticles PANI-SiO2NPs, and preparation of hybrid solution; Step 4: Apply and cure the finishing layer by electrostatic spraying. The finishing liquid is loaded into the electrostatic spray gun for spraying. Then carry out step-by-step curing.

6. A method for preparing a super-hydrophobic interface modified lead-carbon electrode as claimed in claim 4, characterized in that: Step 1: includes the following steps: Step 11: Surface activation of lead powder: Add 5% dilute hydrochloric acid to the lead powder and ultrasonicate it for 15 minutes to remove the surface oxide film and form micron-sized pits. Then, rinse with deionized water until neutral, dry in a vacuum at 60°C for 4 hours, and then place the dried lead powder in a plasma treatment device and treat it at a power of 100 W for 15 minutes under an argon atmosphere. Step 12: Activated carbon modification: Place the activated carbon in a tube furnace and treat it at 500°C for 2 hours under an argon atmosphere. After cooling, pass it through a 200-mesh sieve to remove particle agglomerates. Step 13: Matrix pressing: Lead powder, activated carbon, conductive agent, PTFE emulsion, carbon nanofibers and nanosilver particles are mixed according to the ratio, first stirred at 500 rpm in a high-speed stirrer for 15 minutes, and then ultrasonically treated with an ultrasonic power of 200 W and an ultrasonic time of 15 minutes to form a uniform slurry; the slurry is coated on a lead foil current collector with a coating thickness of 300 μm, and the electrode matrix is ​​obtained by cold pressing at a pressure of 15 MPa and drying at 80°C for 12 hours.

7. A method for preparing a super-hydrophobic interface modified lead-carbon electrode as claimed in claim 5, characterized in that: The preparation method of the micron-sized PbO2-WO3 composite microrod array in step 2 is as follows: the pretreated electrode substrate is used as the working electrode, the platinum sheet is used as the counter electrode, and the saturated calomel electrode is used as the reference electrode. The electrodes are placed in a 0.5MH2SO4 electrolyte containing 0.05M Na2WO4, and oxidized at 1.8V for 20 minutes using a constant potential method to generate PbO2-WO3 composite microrods perpendicular to the substrate surface with a rod density of about 1×10 6 roots / cm².

8. A method for preparing a super-hydrophobic interface modified lead-carbon electrode as claimed in claim 6, characterized in that: The step 3 further comprises: Step 31: Synthesis of FS-GQDs: Add 200 mL of ethanol / water to a three-necked flask, add 2 g of GQD-COOH, and ultrasonically disperse for 30 min. Then, add 1.6 g of FAS-17 and 1.6 g of PFDTES according to the ratio, place in a microwave reactor, set the temperature to 60°C, and react for 30 min. After the reaction, centrifuge, collect the precipitate, and vacuum dry to obtain FS-GQD powder. Step 32: Preparation of PANI-SiO2NPs: In a reaction vessel, disperse 1 g of nano-silica in a solution containing 5 mL of aniline monomer, add 0.5 g of ammonium persulfate as an initiator, and adjust the solution pH to 2-3. Stir the reaction at room temperature for 6 h. After the reaction, centrifuge and collect the precipitate, wash it repeatedly with deionized water and ethanol, and dry it in a vacuum at 60°C for 12 h to obtain PANI-SiO2NPs. Step 33: Preparation of hybrid solution: 5 g of HPS was dissolved in 200 mL of toluene, and 10 g of FS-GQD, 10 g of PANI-SiO2NPs, 0.4 g of mixed nano-titanium dioxide, and 2 mL of ethanolamine were added; first, ultrasonic dispersion was performed in an ultrasonic instrument for 2 h, and then the mixture was transferred to a ball mill and ball milled at 300 rpm for 2 h to form a uniform modified solution with a solid content of 8%, and then allowed to stand for degassing for 30 min.

9. A method for preparing a super-hydrophobic interface modified lead-carbon electrode as claimed in claim 7, characterized in that: The step 4 comprises: Step 41: Electrostatic spraying: Using an electrostatic spraying method, the modification liquid is loaded into an electrostatic spray gun, and a voltage of -50 kV is applied to the electrode surface, and the spraying is performed at a pressure of 0.2 MPa. The distance between the nozzle and the electrode surface is controlled to be 15-20 cm, and the coating thickness is controlled to be 5-8 μm. After a single spraying, pre-drying is performed at 60°C for 10 minutes. Repeat three times until a continuous film layer is formed. Step 42: Step-by-step curing: The coated electrode is first placed in an 80°C oven for pre-curing for 1 hour to initially cross-link the silicon-oxygen bonds between HPS molecules and between HPS and FS-GQDs; then the temperature is raised to 120°C for curing for 2 hours to further promote the cross-linking reaction and allow the HPS trimethoxy groups to fully react with the hydroxyl groups on the PbO2-WO3 surface to form covalent bonds.

10. An adaptive electrolyte circulation system for the super-hydrophobic interface modified lead-carbon electrode according to claim 4, comprising: The invention also includes a pressure sensor; the pressure sensor is installed inside the battery near the electrode position, with an interval of less than 1-2 mm; the temperature sensor is arranged near the PbO2-WO3 composite microrod array; 3-5 temperature sensors are evenly arranged on each square centimeter of electrode area; the concentration sensor is arranged close to the PbO2-WO3 composite microrod array, and 2-3 concentration sensors are arranged on each square centimeter of electrode area; and the control system also includes a control system, which, after receiving the digital signal fed back by the pressure sensor, compares the pressure data with a preset pressure threshold range; and performs a comprehensive analysis based on the temperature data fed back by the temperature sensor and the concentration data fed back by the concentration sensor.

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