Lead-acid battery repair liquid and preparation method and use method thereof

Abstract

The present invention provides a lead-acid battery repair fluid, and its preparation and use methods. The repair fluid comprises the following raw materials: MXene, ammonium acetate, ammonium bicarbonate, sodium ethylenediaminetetraacetate (EDTA), montmorillonite, polymaleic anhydride, sodium polystyrene sulfonate, chloroethyl polyvinylpyridinium salt, polyvinylpyrrolidone (PVP), sodium alginate, and deionized water. The repair fluid can effectively dissolve lead sulfate crystals and form a durable and stable protective film on the electrode plates, thereby regenerating the lead-acid battery while effectively preventing further lead sulfate crystals from adhering to the electrode plates, thereby increasing the battery's service life. Furthermore, the raw materials used in the present invention are safe and harmless to the human body, and the preparation method is simple, efficient, and environmentally friendly.

Description

Technical Field

[0001] The invention belongs to the technical field of lead-acid battery manufacturing, and particularly relates to a lead-acid battery repair fluid and a preparation method and a use method thereof. Background Art

[0002] A lead-acid battery is a type of battery whose electrodes are primarily made of lead and its oxides, and whose electrolyte is sulfuric acid. When discharged, the positive electrode is primarily composed of lead dioxide, and the negative electrode is primarily composed of lead. When charged, both the positive and negative electrodes are primarily composed of lead sulfate. Lead-acid batteries account for over 90% of grid energy storage and backup batteries. The number of lead-acid batteries currently in operation is enormous, and the number of lead-acid batteries scrapped annually is also increasing. Improper disposal of these scrapped lead-acid batteries poses a serious threat to public health and the ecological environment.

[0003] A common mode of lead-acid battery failure is the softening and shedding of the positive active material. The main reason for the softening and shedding of the active material is that as the battery cycle charge and discharge proceeds, the morphology of the positive active material lead dioxide changes from the amorphous state after formation to crystallization and coralization. Therefore, the crystallization or coralization of lead dioxide causes the softening and shedding of the active material. The crystallization and saltization of lead sulfate, the negative plate material, is the main factor in battery scrapping, accounting for more than 90% of the reasons for premature scrapping of lead-acid batteries. To address this problem, the methods used in the prior art include high-current charging repair, high-frequency pulse repair, series repair, and negative pulse repair. However, these currently used methods have various problems, such as easily damaging the electrode plates and difficulty in deeply removing sulfuric acid crystals. Therefore, a repair technology that can perform deep repair without or causing less damage to the electrode plates is urgently needed to solve the above problems. Based on this, the present invention has carried out research on repair agents to more effectively solve the problem of battery regeneration. Summary of the Invention

[0004] The present invention addresses the problems of the prior art and provides a lead-acid battery repair fluid, its preparation method, and its use method. The repair fluid of the present invention can effectively dissolve lead sulfate crystals and form a durable and stable protective film on the electrode plates, thereby regenerating the lead-acid battery while effectively preventing further lead sulfate crystals from adhering to the electrode plates, thereby increasing the battery's service life. The raw materials used in the present invention are safe and harmless to the human body, and the preparation method is simple, efficient, and environmentally friendly.

[0005] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0006] A lead-acid battery repair fluid is prepared by mixing the following raw materials:

[0007] Mxene (Maikoene two-dimensional material), ammonium acetate, ammonium bicarbonate, sodium ethylenediaminetetraacetate (EDTA), montmorillonite, polymaleic anhydride, sodium polystyrene sulfonate, chloroethyl polyvinylpyridinium salt, polyvinylpyrrolidone (PVP), sodium alginate and deionized water.

[0008] During overdischarge or prolonged storage after discharge, lead sulfate particles dissolve in the electrolyte, becoming saturated. These lead sulfate particles recrystallize at low temperatures, precipitating as crystalline lead sulfate. This process, caused by temperature fluctuations, causes the crystals to grow and develop repeatedly on the once-precipitated particles, increasing their size. This lead sulfate exhibits poor conductivity, high resistance, and low solubility and dissolution rate, making it difficult to recover during charging. This leads to reduced capacity and shortened battery life. A normal lead-acid battery forms lead sulfate crystals during discharge, which are relatively easily reduced to lead during charging. However, if the battery is poorly used and maintained, such as through frequent undercharging or overdischarging, a coarse, hard lead sulfate will gradually form on the negative electrode. This lead sulfate is difficult to reduce using conventional charging methods, requiring a high charging voltage. Due to its poor charge acceptance, it produces a large amount of gas during charging. This phenomenon, which typically occurs at the negative electrode, is known as irreversible sulfation. It causes a decrease in battery capacity and can even lead to the end of the battery's life. It is generally believed that this irreversible sulfation is caused by recrystallization of lead sulfate, with the solubility of the coarse crystals decreasing after formation. The recrystallization of lead sulfate causes the crystals to grow larger, which is the result of the tendency of the polycrystalline system to reduce its surface free energy. Therefore, removing the crystallized and insoluble lead sulfate is an important method to extend the life of the battery.

[0009] Therefore, in the present invention, MXene prepared as an electrode material exhibits higher specific capacity and rate performance. Its presence inhibits or even eliminates dendrite formation on the metal negative electrode, extending the service life of rechargeable lithium-ion batteries. Based on this principle, it can also inhibit the formation of lead sulfate dendrites. The ammonium acetate used in the present invention dissolves lead sulfate precipitates. Ammonium bicarbonate has a foaming effect, fully dispersing partially dissolved lead sulfate crystals. The porous and loose structure of montmorillonite can absorb fine lead sulfate crystals, and the pores restrict the further growth of these crystals, making them difficult to dissolve. Sodium ethylenediaminetetraacetate (EDTA), polymaleic anhydride, sodium polystyrene sulfonate, and chloroethyl polyvinylpyridinium salt have a chelating effect, complexing the Pb2+ ions dissolved from the lead sulfate crystals, preventing them from recrystallizing into insoluble crystals. Polyvinylpyrrolidone (PVP), sodium alginate, and deionized water provide a dispersing effect, protecting the dispersed state and preventing the lead sulfate from recrystallizing and agglomerating into large, insoluble crystals. Therefore, the repair liquid of the present invention integrates two-dimensional porous materials, inhibitors, solubilizers, complexing agents, foaming agents, protective agents, and dispersants, which can fully dissolve insoluble large lead sulfate crystals and inhibit them from regenerating into large crystals to reduce battery life.

[0010] Furthermore, the lead-acid battery repair solution comprises the following raw materials in parts by weight:

[0011] 8-15 parts of Mxene, 6-15 parts of ammonium acetate, 1-3 parts of ammonium bicarbonate, 0.5-1 parts of sodium ethylenediaminetetraacetate (EDTA), 3-8 parts of montmorillonite, 1-2 parts of polymaleic anhydride, 0.6-1.5 parts of sodium polystyrene sulfonate, 0.5-0.9 parts of chloroethyl polyvinylpyridinium salt (the main function of this salt is to complex Pb ions, and this substance is a polymer surfactant that can reduce surface tension, fully dissolve lead sulfate and make it less likely to reagglomerate and increase crystallization.), 0.4-0.8 parts of polyvinylpyrrolidone, 0.8-2.5 parts of sodium alginate and 40-85 parts of deionized water.

[0012] Further preferably, 9-12 parts of Mxene, 8-10 parts of ammonium acetate, 2 parts of ammonium bicarbonate, 0.5-0.8 parts of sodium ethylenediaminetetraacetate (EDTA), 3-6 parts of montmorillonite, 1 part of polymaleic anhydride, 0.8-1.2 parts of sodium polystyrene sulfonate, 0.5-0.6 parts of chloroethyl polyvinylpyridine salt, 0.5-0.6 parts of polyvinylpyrrolidone, 0.8-1.0 parts of sodium alginate and 60-80 parts of deionized water.

[0013] Furthermore, the MXene structure is a Ti3C2 phase structure, which is obtained by HF etching of a titanium aluminum carbide MAX phase. MXene with a Ti3C2 phase structure obtained by HF etching of a titanium aluminum carbide MAX phase can be made into a negative electrode material for lithium-ion batteries, inhibiting the formation of crystals.

[0014] Furthermore, the montmorillonite is Lewis acid-modified montmorillonite, and the Lewis acid modification is used to improve the activity of the montmorillonite. The Lewis acid can be anhydrous ZnCl2, anhydrous AlCl3, anhydrous FeCl3, etc.

[0015] Furthermore, the molecular weight of the sodium polystyrene sulfonate is 8×10 4 Dalton, the viscosity is not good when the molecular weight is lower than this value.

[0016] The dispersibility decreases, and the performance of complexing Pb ions deteriorates when the molecular weight exceeds this parameter. Therefore, the present invention preferably uses sodium polystyrene sulfonate with this molecular weight.

[0017] Furthermore, the chloroethyl polyvinyl pyridinium salt has a molecular weight of 30×10 4 The chloroethyl polyvinyl pyridine salt has a molecular weight of 30×10 4 Daltons. Below this molecular weight parameter, the dispersibility and surface tension reduction effects are not ideal, while above this parameter value, the cost increases.

[0018] Furthermore, the polyvinyl pyrrolidone is povidone K90. If the parameter value is lower than this, such as povidone K30 or K60, the dispersibility decreases and it is not easy to disperse.

[0019] Furthermore, the sodium alginate is a variety with a high degree of polymerization (0.35±0.05) Pa·s, and the dispersibility will decrease below this parameter value.

[0020] The present invention also provides a method for preparing the above-mentioned lead-acid battery repair liquid, comprising the following steps:

[0021] (1) Disperse MXene, ammonium acetate, ammonium bicarbonate, sodium ethylenediaminetetraacetate (EDTA), and montmorillonite in deionized water and stir to obtain a dispersion. In this step, high-speed stirring at a speed of 1500-2000 rpm is preferred. Stirring speeds below this range prevent the solid components from being fully mixed and dispersed. Stirring speeds above this range increase the difficulty of mechanical stirring, as the stirring speed approaches the maximum value of high-speed mechanical stirring.

[0022] (2) Dissolve polymaleic anhydride, sodium polystyrene sulfonate, chloroethyl polyvinylpyridinium salt, polyvinylpyrrolidone (PVP), and sodium alginate in deionized water to prepare a solution.

[0023] (3) The dispersion of step (1) is mixed with the solution obtained in step (2), stirred, and then subjected to ultrasonic oscillation.

[0024] Furthermore, the temperature range for controlling the dispersion in step (1) is 20° C. to 50° C., preferably 45° C. Too high a temperature will reduce the activity of the activation solution, while too low a temperature will be detrimental to dispersion.

[0025] Furthermore, the temperature of the solution prepared in step (2) is 40°C-60°C, preferably 50°C.

[0026] Furthermore, in step (3), the ultrasonic oscillation is performed 3-5 times, preferably 5 times, with each oscillation lasting 1-3 minutes, preferably 2 minutes. The total oscillation time is 5-15 minutes. If the number of ultrasonic oscillations is too large, the time and manufacturing cost will be increased, while if the number of ultrasonic oscillations is too small, it will not be conducive to dispersion.

[0027] The present invention also discloses a method for using the above-mentioned lead-acid battery repair liquid. The prepared lead-acid battery regeneration and repair agent is added to the lead-acid battery, ultrasonically oscillated for 1-2 minutes, paused for 1 minute, and then ultrasonically oscillated for 1-2 minutes, for 3-5 times in a row, for charging and activation. This operation is also for full dispersion and activation. Continuous and uninterrupted ultrasonic oscillation increases the risk of damaging the battery. Therefore, a method of multiple oscillations with intervals for a period of time is adopted to fully disperse and activate. Then, the charge and discharge cycle is carried out for 5 cycles and the capacity is tested.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] The present invention uses Mxene, ammonium acetate, ammonium bicarbonate, sodium ethylenediaminetetraacetate (EDTA), and montmorillonite to activate lead sulfate and remove its crystalline structure. A solution prepared by polymaleic anhydride, sodium polystyrene sulfonate, chloroethyl polyvinylpyridinium salt, polyvinylpyrrolidone (PVP), and sodium alginate is then used for complexation to dissolve the lead sulfate crystals. A durable and stable complex protective film is formed on the electrode plate, thereby effectively preventing more lead sulfate crystals from adhering to the electrode plate while regenerating the lead-acid battery, thereby increasing the service life of the battery.

[0030] The preparation process of the present invention is simple, safe, environmentally friendly, easy to scale up industrially, and highly operable. The components cooperate with each other to maximize the effect of complexing, activating, removing crystalline lead sulfate crystals and preventing their regeneration.

[0031] The lead-acid battery repairing liquid prepared by the invention can be widely used in repairing lead-acid batteries and greatly prolongs their service life. DETAILED DESCRIPTION

[0032] In order to more clearly illustrate the embodiments of the present invention, the specific implementation methods will be described below. Obviously, the following descriptions are only some embodiments of the present invention, and those skilled in the art can obtain other implementation methods based on these descriptions without paying creative work.

[0033] Example 1:

[0034] A lead-acid battery repair liquid comprises the following raw materials, measured by weight: 12 parts of Mxene, 10 parts of ammonium acetate, 2 parts of ammonium bicarbonate, 0.5 parts of sodium ethylenediaminetetraacetate (EDTA), 4 parts of montmorillonite, 1 part of polymaleic anhydride, 0.8 parts of sodium polystyrene sulfonate, 0.5 parts of chloroethyl polyvinylpyridinium salt, 0.5 parts of polyvinylpyrrolidone (PVP), 0.8 parts of sodium alginate, and 85 parts of deionized water.

[0035] The preparation method of the above-mentioned lead-acid battery repair liquid comprises the following steps:

[0036] (1) Disperse Mxene, ammonium acetate, ammonium bicarbonate, sodium ethylenediaminetetraacetate (EDTA), and montmorillonite in deionized water and stir at a high speed of 1500 rpm to obtain a dispersion.

[0037] (2) Dissolve polymaleic anhydride, sodium polystyrene sulfonate, chloroethyl polyvinylpyridinium salt, polyvinylpyrrolidone (PVP), and sodium alginate in deionized water to prepare a solution.

[0038] (3) The dispersion of step (1) and the solution prepared in step (2) were mixed, stirred, and then subjected to ultrasonic oscillation for 5 minutes.

[0039] The lead-acid battery repair fluid is used to repair and activate the battery by adding the prepared lead-acid battery regeneration and repair agent to the battery. The battery is then ultrasonically oscillated for 1 minute, followed by a 1-minute pause and then a 1-minute re-oscillation cycle for 5 consecutive times. The battery is then charged and activated. The battery capacity is then tested after 5 charge and discharge cycles.

[0040] Example 2:

[0041] A lead-acid battery repair liquid comprises the following raw materials, measured by weight: 10 parts of Mxene, 8 parts of ammonium acetate, 3 parts of ammonium bicarbonate, 0.6 parts of sodium ethylenediaminetetraacetate (EDTA), 3 parts of montmorillonite, 1.5 parts of polymaleic anhydride, 1 part of sodium polystyrene sulfonate, 0.6 parts of chloroethyl polyvinylpyridinium salt, 0.6 parts of polyvinylpyrrolidone (PVP), 1 part of sodium alginate, and 80 parts of deionized water.

[0042] The preparation method of the above-mentioned lead-acid battery repair liquid comprises the following steps:

[0043] (1) Disperse Mxene, ammonium acetate, ammonium bicarbonate, sodium ethylenediaminetetraacetate (EDTA), and montmorillonite in deionized water and stir at a high speed of 2000 rpm to obtain a dispersion.

[0044] (2) Dissolve polymaleic anhydride, sodium polystyrene sulfonate, chloroethyl polyvinylpyridinium salt, polyvinylpyrrolidone (PVP), and sodium alginate in deionized water to prepare a solution.

[0045] (3) The dispersion of step (1) and the solution prepared in step (2) were mixed, stirred, and then subjected to ultrasonic oscillation for 10 minutes.

[0046] The lead-acid battery repair fluid is used to repair and activate the battery. The prepared lead-acid battery regeneration and repair agent is added to the battery, and ultrasonic vibration is applied for 2 minutes, followed by a 1-minute pause and then a further 2 minutes of ultrasonic vibration, three times in a row, for charging and activation. After 5 charge and discharge cycles, the battery capacity is tested.

[0047] Example 3:

[0048] A lead-acid battery repair liquid comprises the following raw materials, measured by weight: 9 parts of Mxene, 9 parts of ammonium acetate, 1 part of ammonium bicarbonate, 1 part of sodium ethylenediaminetetraacetate (EDTA), 6 parts of montmorillonite, 2 parts of polymaleic anhydride, 1 part of sodium polystyrene sulfonate, 0.5 parts of chloroethyl polyvinylpyridinium salt, 0.5 parts of polyvinylpyrrolidone (PVP), 1 part of sodium alginate, and 66 parts of deionized water.

[0049] The preparation method of the above-mentioned lead-acid battery repair liquid comprises the following steps:

[0050] (1) Disperse Mxene, ammonium acetate, ammonium bicarbonate, sodium ethylenediaminetetraacetate (EDTA), and montmorillonite in deionized water and stir at a high speed of 1800 rpm to obtain a dispersion.

[0051] (2) Dissolve polymaleic anhydride, sodium polystyrene sulfonate, chloroethyl polyvinylpyridinium salt, polyvinylpyrrolidone (PVP), and sodium alginate in deionized water to prepare a solution.

[0052] (3) The dispersion of step (1) and the solution prepared in step (2) were mixed, stirred, and then subjected to ultrasonic oscillation for 5 minutes.

[0053] The lead-acid battery regeneration and repair fluid is used as follows: add the prepared lead-acid battery regeneration and repair agent to a lead-acid battery, ultrasonically vibrate for 2 minutes, rest for 1 minute, and then continue ultrasonically vibrating for 2 minutes, for 5 consecutive times, to charge and activate the battery. After 5 charge and discharge cycles, the battery capacity is tested.

[0054] Comparative Example 1, compared with Example 1, removes the Mxene component and the ammonium acetate component, and the rest is the same as Example 1.

[0055] Comparative Example 2, compared with Example 1, removes polymaleic anhydride, sodium polystyrene sulfonate, and chloroethyl polyvinyl pyridinium salt, and the rest is the same as Example 1.

[0056] Comparative Example 3, compared with Example 1, has the same proportions and ingredients, but omits the ultrasonic oscillation step, and the rest are the same.

[0057] Capacity repair test

[0058] 120 lead-acid batteries (standard capacity of 500HA) that were used for 3 years due to sulfate crystallization were randomly divided into 6 groups, each with 20 batteries. The repair solutions prepared in Examples 1-3 and Comparative Examples 1-3 were added to the grouped batteries (the repair agent was added according to 10% AH of the battery capacity). The batteries were discharged at a rate of 10 hours. After 5 cycles of charge and discharge, the capacity of the repaired batteries was examined, and the capacity repair rate was calculated. The test results are summarized in Table 1 below.

[0059] Table 1

[0060]

[0061] As shown in Table 1, MXene and ammonium acetate play a key role in restoring battery capacity. Maleic anhydride, sodium polystyrene sulfonate, and chloroethyl polyvinylpyridinium salt also play a significant role in restoring battery capacity. Ultrasonic oscillation also significantly promotes battery capacity restoration. All components are indispensable, and the key preparation steps are also important.

[0062] Cycle life test

[0063] 120 scrapped batteries (standard capacity of 500HA) were selected and randomly divided into 6 groups, each with 20 batteries. The repair liquids prepared in Examples 1-3 and Comparative Examples 1-3 were added respectively (the repair agent was added according to 10% AH of the battery capacity). The batteries were continuously discharged at a stable current of 10A for 2 hours and continuously charged at a stable voltage of 15V for 4 hours. Multiple cycles were performed at a temperature of 25°C. The test was terminated when the open circuit voltage of the battery was lower than 10V, and the number of cycles was counted in Table 2.

[0064] Table 2

[0065]

[0066] As shown in Table 2 above, the Mxene component and the ammonium acetate component can significantly enhance the service life of the battery. The introduction of complexing protective agents such as maleic anhydride, sodium polystyrene sulfonate, and chloroethyl polyvinyl pyridinium salt also has a significant effect on the number of cycles. Ultrasonic vibration can enhance the service life of the battery.

[0067] The above description is only a detailed description of the preferred embodiments and principles of the present invention. For ordinary technicians in this field, based on the ideas provided by the present invention, there may be changes in the specific implementation methods, and these changes should also be considered as the scope of protection of the present invention.

Claims

1. A lead-acid battery repair fluid, characterized in that The following materials are mixed: Mxene, ammonium acetate, ammonium bicarbonate, sodium ethylenediaminetetraacetic acid, montmorillonite, polymaleic anhydride, sodium polystyrene sulfonate, chloroethyl polyvinylpyridinium salt, polyvinylpyrrolidone, sodium alginate and deionized water; The materials are calculated by weight as follows: 8-15 parts of Mxene, 6-15 parts of ammonium acetate, 1-3 parts of ammonium bicarbonate, 0.5-1 parts of sodium ethylenediaminetetraacetic acid, 3-8 parts of montmorillonite, 1-2 parts of polymaleic anhydride, 0.6-1.5 parts of sodium polystyrene sulfonate, 0.5-0.9 parts of polyvinyl pyridinium chloride, 0.4-0.8 parts of polyvinyl pyrrolidone, 0.8-2.5 parts of sodium alginate and 40-85 parts of deionized water; The montmorillonite is Lewis acid-modified montmorillonite; The Mxene structure is a Ti3C2 phase structure.

2. A method for preparing the lead-acid battery repair solution according to claim 1, characterized in that Follow these steps: (1) Dispersing Mxene, ammonium acetate, ammonium bicarbonate, sodium ethylenediaminetetraacetate, and montmorillonite in deionized water and stirring to obtain a dispersion; (2) Dissolve polymaleic anhydride, sodium polystyrene sulfonate, chloroethyl polyvinylpyridinium salt, polyvinylpyrrolidone, and sodium alginate in deionized water to prepare a solution; (3) The dispersion obtained in step (1) is mixed with the solution obtained in step (2), stirred, and then subjected to ultrasonic oscillation.

3. The method for preparing the lead-acid battery repair solution according to claim 2, wherein: In step (1), the temperature is controlled in the range of 20°C to 50°C.

4. The method for preparing the lead-acid battery repair solution according to claim 2 or 3, wherein: In step (1), the stirring speed is 1500-2000 rpm.

5. The method for preparing the lead-acid battery repair solution according to claim 2, wherein: In step (2), the temperature of the solution is 40°C-60°C.

6. The method for preparing the lead-acid battery repair solution according to claim 2, wherein: In step (3), ultrasonic oscillation is used for 5-15 minutes.

7. The method for preparing the lead-acid battery repair solution according to claim 2 or 6, wherein: In step (3), ultrasonic oscillation is performed 3-5 times.

8. A method for using a lead-acid battery repair solution, characterized in that: The lead-acid battery repair liquid according to claim 1 or the lead-acid battery repair liquid prepared according to any one of claims 2 to 7 is added to a lead-acid battery, and ultrasonically oscillated to perform charging activation.

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