A pool electrolytic sanitizing electrode and system

Abstract

The application discloses a kind of swimming pool electrolytic disinfection electrode and system, belong to electrochemical water treatment field.The electrode is to adopt asymmetric gradient structure, electrode A is the high-efficiency chlorine production electrode of ultra-thin rGO microporous layer coating;Electrode B is the intelligent management and control electrode of coating phytic acid intercalated layered double hydroxide and reduced graphene oxide composite (LDH-PA@rGO), and adopt lower than 120 ℃ low-temperature curing process.Cooperate EIS monitoring module, when detecting that electrode B impedance is abnormally increased, trigger asymmetric pulse polarity reversal (AIPR): millisecond high-frequency narrow pulse large current is applied to electrode B, using LDH trace dissolution consumes H+ Form local buffer protection phytic acid, while using micro-gas explosion shear force physical descaling.Solve the technical problem that traditional symmetrical electrode frequent reversal leads to coating pulverization, realize on-demand intelligent cleaning, significantly inhibit the generation of chlorate byproduct, electrode speed life is improved by more than 70%, and comprehensive energy consumption is reduced by more than 25%.

Description

Technical Field

[0001] This invention relates to the field of electrochemical water treatment and swimming pool disinfection technology. Specifically, it relates to an electrolytic disinfection electrode with an asymmetric gradient structure, its preparation method, and an asymmetric pulse polarity reversal (AIPR) intelligent control electrolytic disinfection system based on electrochemical impedance spectroscopy (EIS) feedback. Background Technology

[0002] Maintaining water quality in applications with low water change frequency, such as swimming pools and large bathtubs, increasingly relies on continuous and efficient disinfection technologies. Among various technological approaches, electrolytic disinfection, especially systems based on salt chlorination generators, has become the mainstream in the market. Its basic principle is to electrolyze an aqueous solution containing chloride ions (usually water with added salt), generating hypochlorous acid (HOCl), a highly oxidizing agent, at the anode, thereby killing bacteria, viruses, and other microorganisms in the water and achieving long-term disinfection. However, despite the maturity and large-scale commercialization of this technology, it still faces a series of severe technical bottlenecks in practical applications. These issues directly restrict the long-term stability, operational efficiency, and economic viability of the system.

[0003] The mainstream technological paths in the current market are highly convergent. Regarding electrode materials, titanium (Ti)-based coated electrodes with noble metal oxides (mixed metal oxides) are the dominant approach. Common coating systems include RuO2-IrO2 and SnO2-Sb2O5, which exhibit good catalytic activity and stability during chlorination. For applications seeking higher performance, boron-doped diamond electrodes have attracted attention due to their wide potential window and strong oxidation resistance; however, their high cost and manufacturing difficulty limit their widespread adoption in large-scale, low-cost applications such as swimming pools. In terms of control strategies, most commercial systems employ open-loop or semi-open-loop control, i.e., setting fixed operating times or frequencies to perform periodic operations. This design is simple and reliable, but lacks adaptability to changes in water quality, leading to either over-operation resulting in energy waste or under-operation failing to effectively cope with water quality fluctuations.

[0004] Current mainstream technologies face the following three core pain points: Cathode scaling and passivation: In the hard water of the swimming pool, Ca²⁺ and Mg²⁺ readily form CaCO₃ and Mg(OH)₂ scale under the localized high pH environment caused by hydrogen evolution at the cathode. This not only increases ohmic resistance, leading to higher tank voltage and increased energy consumption, but also hinders mass transfer and accelerates electrode passivation.

[0005] Coating degradation due to polarity reversal (PPR): Existing technologies mostly employ passive descaling methods involving periodic polarity switching. For example, CN102918184B discloses an electrode for the electrochemical generation of hypochlorite. This electrode comprises a valve metal substrate coated with a catalytic system consisting of two stacked layers with different compositions and different activities for the generation of hypochlorite from a chloride solution anode. This electrode has a long duration under cathode operating conditions and imparts self-cleaning properties when used in conjunction with periodic polarity reversal with the same electrode. Furthermore, electrode deactivation occurs in two successive steps at the end of its lifespan, allowing for replacement with a significant notice period. However, such conventional symmetrical noble metal oxide (MMO, such as RuO2-IrO2) coatings are highly susceptible to reductive pulverization or peeling off from the titanium substrate when used as a cathode under prolonged hydrogen evolution reduction potential, severely shortening the electrode's lifespan.

[0006] Excessive disinfection byproducts: Under conditions of high current density or local pH imbalance, hypochlorous acid is prone to disproportionation or further oxidation to generate harmful byproducts such as chlorate (ClO3⁻), and the existing electrode structure lacks an in-situ inhibition mechanism.

[0007] For example, CN109790635A discloses an electrolytic water generating device that electrolyzes water containing chloride ions to generate electrolyzed water containing hypochlorous acid. The device includes an electrolytic cell through which the water passes and electrodes disposed within the electrolytic cell. The electrodes have a catalyst layer containing iridium oxide, tantalum oxide, and rhodium oxide. In the catalyst layer, the proportion of rhodium atoms relative to the sum of the number of iridium atoms in the iridium oxide, the number of tantalum atoms in the tantalum oxide, and the number of rhodium atoms in the rhodium oxide is 31% to 60%. This technology attempts to extend the lifespan by adjusting the ratio of Ir, Ta, and Rh, but it remains limited to the technical framework of "symmetrical coating and passive timed acid dissolution for scale removal." Simply introducing scale inhibitors will quickly destroy or wash them away by the conventional acidic reversal environment; using high-temperature sintering to prepare functional coatings will destroy the activity of heat-sensitive scale-inhibiting molecules. Therefore, a systematic and innovative solution that breaks through industry technological inertia is urgently needed. Summary of the Invention

[0008] The purpose of this invention is to overcome the defects of existing swimming pool electrolytic disinfection systems, such as easy scaling of electrodes, short lifespan due to coating reduction and powdering caused by polarity reversal, and accumulation of chlorate byproducts. The invention provides an asymmetric intelligent electrolytic disinfection electrode and closed-loop control system that has long-lasting self-cleaning, resistance to reduction and powdering, and the ability to inhibit byproducts in situ.

[0009] The first objective of this invention is to provide a swimming pool electrolytic disinfection electrode pair, which includes a main control high-efficiency chlorine production electrode A and an intelligent scale inhibition and by-product control electrode B, wherein the substrates of electrode A and electrode B are both titanium substrates; the substrates of electrode A and electrode B are both three-dimensional mesh titanium substrates. The electrode A comprises, from the inside out: an IrO2-Ta2O5 protective layer, a RuO2-IrO2 active layer, and a reduced graphene oxide microporous layer; The electrode B comprises, from the inside out: an IrO2-Ta2O5 protective layer, and a functional layer for intelligent scale inhibition and chlorate formation inhibition; The functional layer is composed of a phytic acid intercalated modified layered bimetallic hydroxide, a reduced graphene oxide composite, and a binder.

[0010] Preferably, in the phytic acid intercalation modified layered bimetallic hydroxide, the layered bimetallic hydroxide is Mg-Al-LDH, and the amount of phytic acid intercalation is 20% to 30% of the mass of LDH.

[0011] Furthermore, the amount of rGO coating in the reduced graphene oxide composite is 3% to 8% of the mass of LDH-PA; Preferably, the binder is polyvinylidene fluoride, and the mass ratio of phytic acid intercalated modified layered bimetallic hydroxide and reduced graphene oxide composite to polyvinylidene fluoride is 8:2 to 9:1.

[0012] Preferably, the thickness of the reduced graphene oxide microporous layer in electrode A is 0.5~2μm; and the thickness of the intelligent scale inhibitor and chlorate inhibition functional layer in electrode B is 10~15μm.

[0013] Furthermore, the preparation method of the intelligent scale inhibitor and chlorate-inhibiting functional layer includes the following steps: S1. Disperse Mg-Al-LDH in deionized water, adjust the pH to 4.0~5.0, add phytic acid aqueous solution, stir the reaction at 50~70℃, centrifuge, wash and dry to obtain phytic acid intercalated LDH, denoted as LDH-PA; S2. LDH-PA was ultrasonically dispersed in deionized water, and graphene oxide (GO) aqueous dispersion was added. The mixture was stirred to coat LDH-PA particles with GO. Then a reducing agent was added and the mixture was reacted at 80-100℃ to partially reduce GO to rGO. After centrifugation and drying, phytic acid intercalation modified layered bimetallic hydroxide and reduced graphene oxide composite were obtained, denoted as LDH-PA@rGO composite powder. S3. Disperse LDH-PA@rGO composite powder and PVDF binder in an organic solvent to form a slurry, coat it onto the titanium substrate that has been coated with a protective layer, and dry and cure it at 80~120℃.

[0014] The second objective of this invention is to provide an intelligent electrolytic disinfection system, which includes the swimming pool electrolytic disinfection electrode pair, electrolytic cell, power module and main controller as described above; The main controller includes the following functions: (1) Real-time monitoring: Under normal chlorine production mode, a high-frequency micro-amplitude AC disturbance signal is periodically applied to electrode B to monitor its charge transfer resistance Rct in real time; (2) Intelligent triggering: When the Rct value of electrode B is detected to rise above the set threshold from the initial reference value, the asymmetric pulse polarity reversal AIPR cleaning mode is triggered. (3) AIPR execution: switch the polarity to make electrode B the anode, and apply a high-frequency narrow pulse large current with a duration of 50~150 ms to electrode B; (4) Rapid recovery: After the pulse cleaning is completed, the system immediately resumes normal polarity and continues to produce chlorine.

[0015] Preferably, the set threshold is 30% to 50% of the initial baseline Rct value.

[0016] Preferably, the equivalent current density of the high-frequency narrow-pulse high current is 3 to 5 times that of the conventional chlorine production current density.

[0017] Preferably, the intelligent electrolytic disinfection system is used in the electrolytic disinfection of swimming pools, large bathtubs, or landscape water bodies.

[0018] The beneficial effects of this invention are: This invention introduces LDH-PA@rGO into the electrolytic electrode. rGO not only overcomes the technical barrier that prevents LDH from being used in electrodes due to its insulation properties, but its flexible encapsulation also prevents LDH from detaching under fluid erosion. A low-temperature curing process, not exceeding 120°C, perfectly preserves the chelating activity of phytic acid and the layered structure of LDH.

[0019] Breaking away from the existing fixed-cycle PPR technology that relies on strong acids to dissolve hard scale, this innovative AIPR strategy utilizes millisecond-level pulsed acidic shock mode. This mode preferentially causes micro-dissolution (Mg²⁺ / Al³⁺ leaching) of the LDH layer, consuming H⁺ and creating a local micro-environment buffer. This perfectly protects the internally intercalated phytic acid from being instantly destroyed by the strong acid. Simultaneously, the instantaneously released O₂ / Cl₂ microbubbles generate "micro-explosion" shear force on the rGO surface, physically loosening the scale layer. The released Mg²⁺ / Al³⁺ also forms flocs to adsorb organic impurities in the water, achieving a triple self-cleaning effect of "chemical buffering, physical micro-explosion, and flocculation adsorption."

[0020] The asymmetric structure features a precise division of labor. The ultrathin rGO layer of electrode A accelerates Cl⁻ mass transfer and promotes bubble desorption, maintaining high initial current efficiency. Electrode B is dedicated to scale inhibition and byproduct control. The alkaline plate of LDH can capture and ion exchange ClO3⁻ in situ. Combined with the reducing properties of phytic acid, it significantly inhibits chlorate formation, meeting stringent environmental standards (such as German DIN19643).

[0021] The closed-loop feedback based on EIS avoids blind and frequent reversals, reduces the time the electrode is at the cathode reduction potential, and fundamentally inhibits the reduction and pulverization of the noble metal coating. Combined with experimental data, the electrode lifespan is increased by more than 70%, and the overall energy consumption is reduced by more than 25%. Attached Figure Description

[0022] Figure 1 Comparison of the tank voltage variation curves of Example 3 and the comparative example during 500 hours of operation test. Detailed Implementation

[0023] The embodiments described below are merely some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the technical concepts and practical guidance described in the embodiments of the present invention without creative effort are within the scope of protection of the present invention. All raw materials in the specific embodiments are commercially available or conventionally synthesized.

[0024] Example 1: Preparation of LDH-PA@rGO smart composite powder Weigh 5.0g of Mg-Al-CO3 LDH (Mg / Al molar ratio = 3:1) and disperse it in 100mL of deionized water. Adjust the pH to 4.5 with 0.1M HCl.

[0025] 2.0 g of phytic acid (50 wt% aqueous solution) was added, and the mixture was stirred at 60 °C under nitrogen protection for 6 hours. After centrifugation, washing, and drying at 60 °C, phytic acid-intercalated LDH (LDH-PA) was obtained. XRD analysis showed that its interlayer spacing d... 003 Expanding from 0.76nm to 1.48nm, TGA showed that the phytic acid content was approximately 24wt%.

[0026] 2.0 g LDH-PA was ultrasonically dispersed in 100 mL of deionized water. 50 mL of GO aqueous dispersion (concentration 2 mg / mL, GO:LDH mass ratio approximately 1:20) was added, and the mixture was stirred for 30 min to ensure that GO uniformly coated the LDH-PA particles.

[0027] 0.1 g of vitamin C (L-AA) was added as a mild reducing agent, and the mixture was stirred at 90 °C for 2 hours to partially reduce GO to rGO. After centrifugation, washing, and vacuum drying at 60 °C, LDH-PA@rGO composite powder was obtained. Its conductivity was measured using the four-probe method to be ≥65 S / m.

[0028] Example 2: Preparation of an asymmetric electrode pair (electrode A and electrode B) Substrate pretreatment: The three-dimensional mesh titanium plate (purity >99.5%) was ultrasonically degreased with acetone, heat-treated in air at 550℃ for 2 hours, and then acid-etched in 25wt% H2SO4 (containing 5g / L dissolved titanium) at 85℃ for 2 hours. It was then washed with water and dried for later use.

[0029] Protective and active layer coating (shared by electrodes A and B): Using the traditional thermal decomposition method, an IrO2-Ta2O5 protective layer (approximately 1 μm) and a RuO2-IrO2 active layer (approximately 5 μm, Ru:Ir ratio 7:3) are sequentially coated and sintered on the titanium substrate, with a total noble metal loading of approximately 4 g / m².

[0030] Preparation of rGO microporous layer of electrode A: The rGO dispersion (containing 0.5wt% Nafion solution) was sprayed onto the above substrate and dried at 80℃ to form an ultrathin, superhydrophilic rGO porous layer with a thickness of about 1.5μm.

[0031] Preparation of the smart functional layer of electrode B: The LDH-PA@rGO composite powder prepared in Example 1 was dispersed in NMP at a mass ratio of 8.5:1.5 with PVDF and stirred for 4 hours to form a uniform slurry. This slurry was then uniformly sprayed onto the substrate treated in step 2, pre-dried at 60°C for 30 min, and subsequently vacuum-dried at 110°C for 2 hours. The final functional layer thickness was approximately 12 μm.

[0032] Example 3: Operation of AIPR Intelligent Electrolysis Disinfection System Based on EIS Feedback Electrode A (as the main anode) and electrode B (as the main cathode) prepared in Example 2 were assembled in an unseparated electrolytic cell. The electrolyte was simulated hard water from a swimming pool: 3000 ppm NaCl, 400 ppm Ca²⁺ (calculated as CaCO₃), 50 ppm Mg²⁺, and the temperature was 30 ± 1 °C.

[0033] Normal mode: Constant current density 300A / m² operation.

[0034] Monitoring and Triggering: The main controller applies a 10kHz, 10mV AC disturbance to electrode B every 2 hours and fits the EIS data to obtain Rct. When Rct increases by 40% from the initial value, AIPR is triggered.

[0035] AIPR execution: polarity reversal, electrode B becomes the anode. A high-frequency, narrow-pulse high current (equivalent current density 1200 A / m²) is applied for 100 ms, followed immediately by restoration of normal polarity.

[0036] Proportional Design Comparative Example 1: A double-layer RuO2-IrO2 symmetrical electrode was used, and the control system was set to force a 5-minute polarity reversal every 60 minutes.

[0037] Comparative Example 2: The electrode structure is the same as that of Comparative Example 1, but after being coated with LDH-PA slurry, it is sintered and cured at 450°C.

[0038] Comparative Example 3: Electrodes A and B of Embodiment 2 of the present invention are used, but the control system adopts the same strategy as Comparative Example 1, which forces a 5-minute reversal every 60 minutes, without EIS feedback and pulse control.

[0039] Performance testing and experimental data verification Simulated hard water operation test: The electrolyte is 3000ppm NaCl, 400ppm Ca²⁺ (calculated as CaCO3), and 50ppm Mg²⁺. The temperature is 30±1℃, the constant current density is 300A / m², and the continuous operation is 500 hours (with AIPR pulse cleaning triggered once every 4 hours during the period).

[0040] Accelerated life test: According to GB / T20853-2007, in 1M H2SO4 solution, at a current density of 2A / cm² (20000A / m²) and a temperature of 40℃, the failure time when the cell voltage rises to the initial voltage +10V is recorded.

[0041] Under the same simulated hard water conditions, the above-mentioned embodiments and comparative examples were subjected to a 500-hour continuous operation test, and the results are shown in Table 1 below: Cathode scaling (mg / cm²) 15.2 8.5 4.1 1.6 Slot voltage increment (V) +2.45 +1.10 +0.65 +0.18 <![CDATA[Concentration of electrolyte ClO3⁻ (mg / L)]]> 85.4 62.1 48.5 11.2 Accelerated life testing 185h 110h 210h 325h <![CDATA[Comprehensive energy consumption (kWh / kg Cl2)]]> 5.8 5.1 4.6 4.2 The test data above show that the scaling amount in Example 3 is only 10.5% of that in Comparative Example 1, and the tank voltage shows almost no attenuation. This proves that LDH-PA@rGO can accurately release phytic acid chelates Ca²⁺ at high pH at the cathode, and that rGO provides a stable conductive network, avoiding localized overheating and coating peeling caused by insulation in pure LDH (Comparative Example 2).

[0042] Comparative Example 2 suffered from a shorter lifespan than Comparative Example 1 due to the destruction of its phytic acid structure during high-temperature sintering and the lack of rGO protection. Example 3 exhibited an accelerated lifespan of 325 hours (a 75% improvement over Comparative Example 1). The electrode in Comparative Example 1 showed obvious microcracks on its surface after 500 hours; while the LDH-PA@rGO layer structure on the surface of electrode B in Example 3 remained intact. This demonstrates that the flexible buffering effect of rGO effectively absorbed the stress during polarity switching, protecting the underlying active layer.

[0043] The ClO3⁻ concentration in Example 3 was only 11.2 mg / L, far below the 30 mg / L limit specified in the German standard DIN19643. This is attributed to the in-situ ion exchange capture of ClO3⁻ by the basic sites of the LDH layer, and the weak reduction effect of P(III) in phytic acid, which are functions that existing symmetric MMO electrodes do not possess at all.

[0044] Although Comparative Example 3 used the same smart electrode as the present invention, the fixed-cycle strong acid reversal caused irreversible structural collapse of the LDH layer after 200 hours, resulting in a precipitous drop in scale inhibition performance. In contrast, the AIPR strategy in Example 3 ensures that EIS monitoring is triggered only "when needed"; and the instantaneous microbubble "micro-explosion" shear force generated by the 100ms narrow pulse high current, combined with the local pH buffer formed by the consumption of H⁺ from the trace dissolution of LDH, achieves a perfect combination of scale removal and protective layer function. Figure 1 The graph shows a comparison of the incremental changes in tank voltage during the 500-hour operation test.

[0045] Example 4: Optimal Formulation Design of LDH-PA@rGO Composite Material Formula 1: Phytic acid (PA) intercalation amount is 20% of LDH mass; rGO coating amount is 3% of LDH-PA mass; the mass ratio of LDH-PA@rGO to PVDF in the slurry is 8:2.

[0046] Formula 2: Phytic acid (PA) intercalation amount is 25% of LDH mass; rGO coating amount is 5.5% of LDH-PA mass; the mass ratio of LDH-PA@rGO to PVDF in the slurry is 8.5:1.5.

[0047] Formula 3: Phytic acid (PA) intercalation amount is 30% of LDH mass; rGO coating amount is 8% of LDH-PA mass; the mass ratio of LDH-PA@rGO to PVDF in the slurry is 9:1.

[0048] Comparative formulation design Comparative formulation 1: Phytic acid (PA) intercalation amount is 10% of LDH mass; rGO coating amount is 5.5%; PVDF content is 15%.

[0049] Comparative formulation 2: Phytic acid (PA) intercalation amount 25%; rGO coating amount 1% of LDH-PA mass; PVDF content 15%.

[0050] Comparative formulation 3: Phytic acid (PA) intercalation amount 25%; rGO coating amount 5.5%; LDH-PA@rGO to PVDF mass ratio in the slurry is 7:3.

[0051] For the preparation of the asymmetric electrode pair, the LDH-PA@rGO composite powder prepared by formulations 1-3 in Example 4 and Comparative formulations 1-3 was dispersed with the binder PVDF in NMP and stirred for 4 hours to form a uniform slurry. This slurry was then uniformly sprayed onto the treated substrate, pre-dried at 60°C for 30 min, and subsequently vacuum-dried at 110°C for 2 hours, ultimately forming a functional layer with a thickness of approximately 12 μm.

[0052] Table 2. Key performance comparison data between the formulation and the control formulation. Cathodic scale deposition over 500 hours (mg / cm²) 2.1 1.6 1.9 6.8 2.0 1.8 500h tank voltage increment (V) 0.25 0.18 0.22 0.85 1.25 0.95 <![CDATA[Concentration of electrolyte ClO3⁻ (mg / L)]]> 18.5 11.2 14.8 45.2 15.5 16.0 Accelerated lifespan (h) 280 325 305 210 145 185 The experimental data in Table 2 show that the smart functional layers prepared by formulations 1-3 all exhibit excellent comprehensive performance in their electrode B structures. The scaling amount is less than 3.0 mg / cm², the cell voltage increment is less than 0.3V, and the chlorate concentration is less than 20 mg / L, meeting the stringent requirement of less than 30 mg / L in the German DIN19643 standard. Furthermore, the accelerated life is greater than 250 hours. However, when the component ratio exceeds a certain range, as in comparison to formulation 1, due to insufficient phytic acid intercalation, the chelating agent released between the LDH layers cannot effectively capture the high local concentration of Ca²⁺ at the cathode, leading to a surge in scaling to 6.8 mg / cm². Moreover, without the aid of phytic acid's reducing properties, the chlorate concentration soars to 45.2 mg / L, severely exceeding the standard. Compared to formulation 2, the low rGO content prevents the formation of a continuous conductive network between LDH-PA particles, leading to a significant increase in the overall resistance of the functional layer (tank voltage increment as high as 1.25V). Simultaneously, the lack of flexible physical encapsulation by rGO makes LDH prone to peeling under the fluid shearing of AIPR pulses, resulting in a precipitous drop in lifetime to 145 hours. Similarly, compared to formulation 3, the excessively high proportion of the insulating binder PVDF severely blocks the microporous structure of the functional layer, hindering the ion transport of Cl⁻ and OH⁻, resulting in severe polarization (voltage increment of 0.95V) and a significant decrease in current efficiency, also shortening the lifetime to 185 hours.

[0053] The present invention has been described in detail above with reference to the embodiments. It should also be noted that the specific technical features described in the above embodiments can be combined and modified in any suitable manner without contradiction. The present invention will not further describe all possible combinations. Furthermore, other variations and combinations based on the various technical features of the present invention should also be considered as part of the content disclosed in this invention and fall within the protection scope of this invention.

Claims

1. A pair of electrolytic sanitizing electrodes for a swimming pool, characterized in that, It includes a main control high-efficiency chlorine production electrode A and an intelligent scale inhibition and by-product control electrode B, wherein the substrates of electrode A and electrode B are both titanium substrates. The electrode A comprises, from the inside out: an IrO2-Ta2O5 protective layer, a RuO2-IrO2 active layer, and a reduced graphene oxide microporous layer; The electrode B comprises, from the inside out: an IrO2-Ta2O5 protective layer, and a functional layer for intelligent scale inhibition and chlorate formation inhibition; The functional layer is composed of a phytic acid intercalated modified layered bimetallic hydroxide, a reduced graphene oxide composite, and a binder.

2. The swimming pool electrolytic sanitization electrode pair of claim 1, wherein, In the phytic acid intercalation modified layered bimetallic hydroxide, the layered bimetallic hydroxide is Mg-Al-LDH, and the intercalation amount of phytic acid is 20%~30% of the mass of LDH.

3. The swimming pool electrolytic sanitization electrode pair of claim 2, wherein, The amount of rGO coating in the reduced graphene oxide composite is 3% to 8% of the mass of LDH-PA.

4. The swimming pool electrolytic sanitization electrode pair of claim 1, wherein, The binder is polyvinylidene fluoride, and the mass ratio of phytic acid intercalated modified layered bimetallic hydroxide and reduced graphene oxide composite to polyvinylidene fluoride is 8:2 to 9:

1.

5. The swimming pool electrolytic sanitization electrode pair of any one of claims 1-4, wherein, The thickness of the reduced graphene oxide microporous layer in electrode A is 0.5~2μm; the thickness of the intelligent scale inhibitor and chlorate inhibition functional layer in electrode B is 10~15μm.

6. The swimming pool electrolytic sanitization electrode pair of claim 5, wherein, The method for preparing the intelligent scale inhibitor and chlorate-inhibiting functional layer includes the following steps: S1. Disperse Mg-Al-LDH in deionized water, adjust the pH to 4.0~5.0, add phytic acid aqueous solution, stir the reaction at 50~70℃, centrifuge, wash and dry to obtain phytic acid intercalated LDH, denoted as LDH-PA; S2. LDH-PA was ultrasonically dispersed in deionized water, and graphene oxide (GO) aqueous dispersion was added. The mixture was stirred to coat LDH-PA particles with GO. Then a reducing agent was added and the mixture was reacted at 80-100℃ to partially reduce GO to rGO. After centrifugation and drying, phytic acid intercalation modified layered bimetallic hydroxide and reduced graphene oxide composite were obtained, denoted as LDH-PA@rGO composite powder. S3. Disperse LDH-PA@rGO composite powder and PVDF binder in an organic solvent to form a slurry, coat it onto the titanium substrate that has been coated with a protective layer, and dry and cure it at 80~120℃.

7. An intelligent electrolytic disinfection system characterized in that, Includes the pool electrolytic disinfection electrode pair, electrolytic cell, power module and main controller as described in claim 5; The main controller includes the following functions: (1) Real-time monitoring: Under normal chlorine production mode, a high-frequency micro-amplitude AC disturbance signal is periodically applied to electrode B to monitor its charge transfer resistance Rct in real time; (2) Intelligent triggering: When the Rct value of electrode B is detected to rise above the set threshold from the initial reference value, the asymmetric pulse polarity reversal AIPR cleaning mode is triggered. (3) AIPR execution: switch the polarity to make electrode B the anode, and apply a high-frequency narrow pulse large current with a duration of 50~150 ms to electrode B; (4) Rapid recovery: After the pulse cleaning is completed, the system immediately resumes normal polarity and continues to produce chlorine.

8. The intelligent electrolytic disinfecting system of claim 7, wherein, The set threshold is 30% to 50% of the initial baseline Rct value.

9. The intelligent electrolytic disinfection system according to claim 7, characterized in that, The equivalent current density of the high-frequency narrow pulse large current is 3-5 times of the conventional chlorine production current density.

10. The intelligent electrolytic disinfection system according to claim 7, applied in electrolytic disinfection of swimming pools, large bathtubs or landscape water bodies.

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