Method for solving problems of softening and falling of positive active material of lead-acid storage battery or battery pack

Abstract

The invention discloses a method for solving the problems of softening and falling of a positive active material of a lead-acid storage battery or a battery pack. The method comprises the following steps: reversing, repairing, improving and eliminating the problems of softening and falling of the positive active material; the method comprises the following steps: carrying out polarity reversal and subsequent charging or charge-discharge operation on the positive electrode and the negative electrode of the lead-acid storage battery or / and the lead-acid storage battery pack; or converting the positive electrode or the positive electrode active material of the lead-acid storage battery into lead, and then converting lead into PbO2; or the positive electrode or the positive electrode active substance of the lead-acid storage battery is converted into lead or subjected to a negative electrode electrochemical reaction, and the negative electrode or the negative electrode active substance is converted into PbO2 or subjected to a positive electrode electrochemical reaction. The method disclosed by the invention can be used for reversing, repairing, improving and eliminating the problems of softening and falling of the positive active material of the lead-acid storage battery or the battery pack, and prolonging the service life of the lead-acid storage battery or the battery pack.

Description

Technical Field

[0001] The invention relates to a method for solving the problem of lead-acid storage battery or battery pack, and in particular to a method for solving the problem of softening and falling off of positive electrode active material of lead-acid storage battery or battery pack. Background Art

[0002] Lead-acid batteries or battery packs have been widely used for many years due to their low manufacturing cost, high performance / price ratio, safety, stability and recyclability, and they occupy the leading position in the secondary battery market sales share. However, in terms of performance, lead-acid batteries or battery packs have the disadvantages of low specific energy and short service life. At present, the specific energy of lead-acid batteries or battery packs in application is about 20-40Wh / kg, the cycle life is about 150-1500 times, and the floating charge life is about 5-20 years. There are many factors that affect the service life of lead-acid batteries or battery packs. The main and common battery or battery pack failure modes that lead to the end of the service life of lead-acid batteries or battery packs include softening and shedding of positive active materials, etc. Summary of the invention

[0003] The technical problem to be solved by the present invention is to provide a method for solving the softening and falling off problems of the positive active material of the lead-acid battery. The solution includes: reversing, repairing, improving and eliminating the softening and falling off problems of the positive active material.

[0004] The service life includes but is not limited to one or more of cycle life and floating charge life.

[0005] The lead-acid battery or battery pack, that is, a lead-acid battery or a lead-acid battery pack.

[0006] In order to solve the above technical problems, the method provided by the present invention for solving the problem of softening and falling off of the positive active material of the lead-acid battery or battery pack comprises: reversing the polarity of the positive electrode and the negative electrode of the lead-acid battery or / and the lead-acid battery pack and then performing charging or charge-discharging operations, so that the softening and falling off of the positive active material of the lead-acid battery that has occurred is reversed, repaired, improved, or eliminated;

[0007] Alternatively, the method for solving the problem of softening and falling off of the positive active material of the lead-acid battery or battery pack comprises: converting the positive electrode or the positive active material of the lead-acid battery into lead, and then converting the lead into PbO2, so that the softening and falling off of the positive active material of the lead-acid battery that has occurred is reversed, repaired, improved, and eliminated;

[0008] Alternatively, the method for solving the problem of softening and falling off of positive active materials in lead-acid batteries or battery packs includes: converting the positive electrode or positive active material of the lead-acid battery into lead or performing a negative electrode electrochemical reaction, converting the negative electrode or negative electrode active material into PbO2 or performing a positive electrode electrochemical reaction, so as to reverse, repair, improve, and eliminate the softening and falling off problem of the positive active material in the lead-acid battery that has occurred.

[0009] Alternatively, the method for solving the softening and shedding problem of the positive active material of the lead-acid battery or battery pack comprises: reversing the polarity of the positive electrode and the negative electrode of the lead-acid battery or / and the lead-acid battery pack and then performing a charging or charging and discharging operation, wherein the operation is performed or performed ≥1 times; and after the operation is performed ≥1 times, the softening and shedding problem of the positive active material of the lead-acid battery is reversed, repaired, improved, eliminated, or / and the battery capacity of the lead-acid battery whose capacity decay is reduced or whose life is terminated is improved or increased;

[0010] Alternatively, the method for solving the problem of softening and falling off of the positive active material of the lead-acid battery or battery pack comprises: causing the electrode of the lead-acid battery or / and the lead-acid battery pack to undergo polarity reversal, and after the polarity reversal, causing the electrode that has undergone the polarity reversal to undergo the following electrochemical reactions: causing the electrode that was the positive electrode before the polarity reversal to undergo a lead-acid battery negative electrode reaction after the polarity reversal, causing the lead oxide, basic lead sulfate, and lead sulfate contained in the electrode that was the positive electrode before the polarity reversal to undergo an electrochemical reduction reaction after the polarity reversal, and causing the electrode that was the negative electrode before the polarity reversal to undergo a lead-acid battery positive electrode reaction after the polarity reversal, one or more of the following; it is also characterized in that the method is implemented on the lead-acid battery or / and the lead-acid battery pack for ≥1 times, and after the operation is performed for ≥1 times, the softening and falling off of the positive active material of the lead-acid battery is reversed, repaired, improved, or / and the battery capacity of the lead-acid battery with reduced capacity decay and terminated life is improved or increased.

[0011] The polarity reversal of the positive electrode and the negative electrode and the subsequent charging or charge-discharging operation, that is, the polarity reversal of the positive electrode and the negative electrode, and after the polarity reversal, the charging or charge-discharging operation is performed on the electrode that has undergone the polarity reversal.

[0012] The polarity of the positive or negative electrode of the lead-acid battery or battery pack includes the positivity (positive electrode properties) or negativity (negative electrode properties) of the electrode of the lead-acid battery or battery pack. The positive characteristics of the electrode generally include that the electrode reaction occurring on the electrode is a positive electrode reaction and the electrode potential is relatively high. The negative characteristics of the electrode generally include that the electrode reaction occurring on the electrode is a negative electrode reaction and the electrode potential is relatively low. The polarity reversal refers to that the polarity of the original positive electrode changes from positive to negative or / and the polarity of the original negative electrode changes from negative to positive.

[0013] The electrode that has undergone polarity reversal is charged or charged and discharged, that is, the electrode that is a positive electrode before polarity reversal and a negative electrode after polarity reversal is charged or charged and discharged as a negative electrode, and the electrode that is a negative electrode before polarity reversal and a positive electrode after polarity reversal is charged or charged and discharged as a positive electrode. The former causes a negative electrode reaction of a lead-acid battery to occur on the electrode, and the latter causes a positive electrode reaction of a lead-acid battery to occur on the electrode.

[0014] The electrode that has undergone polarity reversal is charged or charged and discharged, wherein the amount of electricity charged or charged and discharged is generally more than 0.5 times the rated capacity of the electrode.

[0015] The method of performing polarity reversal on the positive and negative electrodes of a lead-acid battery or battery pack and subsequent charging or charge-discharging operations is characterized in that the positive and negative electrodes of the lead-acid battery or battery pack that performs or is subjected to the polarity reversal on the positive and negative electrodes and subsequent charging or charge-discharging operations are both common positive and negative electrodes (i.e., electrodes that are common to both the positive and negative electrodes). The common positive and negative electrodes can be used as both positive and negative electrodes in the lead-acid battery or battery pack, or some electrodes can be used as positive electrodes and some electrodes can be used as negative electrodes, or during the operation or use of the lead-acid battery or battery pack, the common positive and negative electrodes can be used as positive electrodes at some times and as negative electrodes at other times, or one or more of the following can be used; when constituting the positive and negative electrodes of a lead-acid battery or battery pack, the common positive and negative electrodes include, but are not limited to, electrodes having the same active substance or the same active substance as each other. The invention relates to universal positive and negative electrodes with the same quality formula, universal positive and negative electrodes that are equivalent to each other, and universal positive and negative electrodes of the same kind; the mutual equivalence means that after being formed or charged and discharged, the electrodes have or show the same functions and performances during the operation or use of the lead-acid battery or battery pack without considering the error factors; the universal positive and negative electrodes of the same kind refer to those universal positive and negative electrodes that are the same as each other before being formed or charged and discharged, and can form the positive electrode or negative electrode after being formed or charged and discharged; the universal positive and negative electrodes that are the same as each other before being formed or charged and discharged means that, without considering the manufacturing errors generated when manufacturing the electrodes, before being formed or charged and discharged, two or more electrodes are completely identical in all electrode compositions and manufacturing aspects (such as electrode structure, shape, size, formula, material, manufacturing process, etc.).

[0016] The polarity reversal of the positive and negative electrodes of the lead-acid battery or battery pack and the subsequent charging or charge-discharging operation can be automatically or / and manually achieved through a circuit, and the circuit has the function of polarity reversal or polarity reversal of the positive and negative electrodes of the lead-acid battery or / and the lead-acid battery pack and the subsequent charging or charge-discharging operation, and the total cumulative number of polarity reversal or polarity reversal of the positive and negative electrodes of the lead-acid battery or / and the lead-acid battery pack and the subsequent charging or charge-discharging operation is ≥1 time.

[0017] The method for the circuit to realize or implement the positive and negative polarity reversal or polarity reversal and subsequent charging or charging and discharging operation on the lead-acid battery or / and the lead-acid battery pack includes: reverse polarity charging of the lead-acid battery or battery pack.

[0018] The method for realizing reverse polarity charging of a lead-acid battery or / and a lead-acid battery pack by the circuit includes realizing polarity reversal of the positive and negative poles of the lead-acid battery or battery pack or polarity reversal and subsequent charging or charging and discharging operations by reversing the polarity of the output terminal of the circuit connected to the electrode of the lead-acid battery or battery pack and performing charging or charge-discharging operations on the lead-acid battery or battery pack after the polarity reversal.

[0019] The polarity reversal of the positive and negative electrodes of the lead-acid battery or battery pack and the subsequent charging or charge-discharging operation is also characterized in that the function of the circuit can be started, stopped or paused by automatic or / and manual or manual switching, so that the circuit starts, stops or pauses the polarity reversal or polarity reversal of the positive and negative electrodes of the lead-acid battery or / and the lead-acid battery pack and the subsequent charging or charge-discharging operation.

[0020] The lead-acid batteries or / and lead-acid battery packs to which the method for improving or extending the service life of a lead-acid battery or / and lead-acid battery pack or the method for reversing the polarity of the positive and negative electrodes of the lead-acid battery or / and lead-acid battery pack and the subsequent charging or charging and discharging operation of the present invention are applied include flat grid type, tubular type, winding type, bipolar type, horizontal lead cloth type, foam grid type, column type, and lead-acid batteries or battery packs with stable void electrodes, and also include valve-regulated sealed lead-acid batteries or battery packs, colloidal lead-acid batteries or battery packs, lead-carbon batteries or battery packs, supercapacitor-lead-acid batteries (referred to as super batteries) batteries or battery packs, and hybrid lead-acid battery packs formed by mixing and connecting these types of lead-acid batteries, as well as other various types of lead-acid batteries or battery packs.

[0021] The method for improving or extending the service life of a lead-acid battery or a battery pack of the present invention can be applied to a lead-acid battery or a battery pack, a circuit or charging and discharging device of a lead-acid battery or a battery pack, and a formation process during the repair, regeneration or production of a lead-acid battery or a battery pack.

[0022] Beneficial Effects

[0023] The method disclosed in the present invention for solving the problem of softening and falling off of positive active materials in lead-acid storage batteries or battery packs can reverse, repair, improve and eliminate the problem of softening and falling off of positive active materials in lead-acid storage batteries or battery packs. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a data diagram of the working discharge capacity and working discharge termination voltage of the lead-acid battery in the cyclic charge and discharge operation of the embodiment 2 of the present invention.

[0025] Figure 2 It is a data diagram of the working discharge capacity and working discharge termination voltage of the lead-acid battery in the cyclic charge and discharge operation of Example 3 of the present invention.

[0026] Figure 3 This is a data diagram of the working discharge capacity and working discharge termination voltage of the lead-acid battery pack in the cyclic charge and discharge operation of the fourth embodiment of the present invention.

[0027] Figure 4 It is a current and voltage data diagram of the lead-acid battery pack of Example 4 of the present invention during the 23rd to 28th cycle charge and discharge operation process and the single positive and negative polarity reversal interspersed during the process and the subsequent charging or charging and discharging operation process.

[0028] The reference numerals in the figures are described as follows: DETAILED DESCRIPTION

[0029] The technical content, features and effects of the present invention are further described in detail below in conjunction with specific embodiments.

[0030] Example 1

[0031] The lead-acid battery of the present embodiment is a flat grid lead-acid battery with a rated capacity of 2.32Ah (2h rate, 25°C) and a rated voltage of 2V. Its cyclic charge and discharge operation (hereinafter referred to as cyclic operation) is as follows: constant current charging at a rate of 0.2 (rated capacity, hereinafter the same), and when the voltage reaches 2.65V, constant voltage charging at 2.65V, the total time of two charges is 6 hours and 24 minutes, and then discharged at a rate of 2h and 80% DOD (depth of discharge), and then the above-mentioned charge and discharge process is repeated, that is, the above-mentioned charge and discharge cycle is used for operation, and the working environment temperature is 25±1°C. In the cyclic charge and discharge operation and polarity reversal and subsequent charging or charge and discharge operation of the battery of the present embodiment, the interference of factors such as loss of fluid, open circuit, short circuit, mechanical damage, and test failure on the implementation process and implementation results of the present embodiment is eliminated or prevented.

[0032] When the remaining capacity of the lead-acid battery of this embodiment (the amount of electricity that can be discharged by the battery according to the working discharge system, the same below) is 7.3% of its rated capacity (after inspection, it is found that the positive electrode active material softens and falls off, resulting in the attenuation of the discharge capacity of the battery of this embodiment), the positive and negative electrode polarity reversal and subsequent charging or charging and discharging operations of the present invention are started (for the sake of clarity, the positive electrode and negative electrode of the lead-acid battery of this embodiment are named electrode group A and electrode group B, the same below), including the following steps:

[0033] 1) Discharge and first polarity reversal: Stop the battery (at this time, the battery is in the constant voltage charging stage during operation), use a charge and discharge device to force discharge the lead-acid battery of this embodiment at a current of 0.5 times the rate (1164 mA), so that the battery voltage drops from 2.65V when the battery stops working to 0V, and finally drops to -0.073V, stop discharging, and then let it stand for 30 minutes (minutes, the same below), and proceed to the next step;

[0034] 2) Reversing the electrode connection after the first polarity reversal: manually connect the positive electrode of the charging and discharging device to the original negative electrode (electrode group B) of the lead-acid battery of this embodiment, and connect the negative electrode of the charging and discharging device to the original positive electrode (electrode group A) of the lead-acid battery of this embodiment, and proceed to the next step;

[0035] 3) Charging: The lead-acid battery of the present embodiment that has completed step 2) is charged with a current of 0.2 times the rate (465.3 mA). When the battery voltage reaches 1.75 V, the charging time is 547 min, and the charging is stopped, and then the next step is performed;

[0036] 4) Discharge and second polarity reversal: While stopping the previous step, start forced discharge of the battery at a current rate of 0.5 times until the battery voltage drops to 0V and finally reaches -0.08V. The discharge takes 9s. Stop discharging and let it stand for 30min before proceeding to the next step.

[0037] 5) Reversing the electrode connection after the second polarity reversal: manually connect the positive electrode of the charging and discharging device to the original positive electrode (electrode group A) of the lead-acid storage battery of this embodiment, and connect the negative electrode of the charging and discharging device to the original negative electrode (electrode group B) of the lead-acid storage battery of this embodiment, in preparation for the next step of charging or charging and discharging;

[0038] 6) Charging: The lead-acid storage battery of this embodiment after completing step 5) is charged with a current of 0.2 times the rate, and the charging is terminated when the voltage reaches 1.75V.

[0039] When step 6) is completed, the battery is simultaneously put into working state and the charging and discharging work is performed with the same working system as before. The working results are shown in Table 1. It can be seen that after the lead-acid battery of this embodiment has undergone the above-mentioned two consecutive polarity reversals and the subsequent charging or charging and discharging operations, the working discharge capacity has been significantly restored. Since the discharge capacity decay of the lead-acid battery of this embodiment is caused by the softening and shedding of the positive active material, the result shows that the polarity reversal and the subsequent charging or charging and discharging operations of this embodiment have significantly reversed the softening and shedding conditions or degree of the positive electrode of the lead-acid battery of this embodiment. Accordingly, if the charging amount of the battery of this embodiment in step 3) of this embodiment is relatively larger (for example, a larger charging current, a longer charging time), it will be beneficial to reverse and restore the softening and shedding conditions of the active material of the original positive electrode (electrode group A) of the battery of this embodiment to a greater extent.

[0040] Table 1

[0041] Rated capacity percentage Before operation, the remaining battery capacity 7.3 The first working discharge capacity of the battery after 2 polarity reversals and subsequent charging or discharging operations 24.9 After 2 polarity reversals and subsequent charging or discharging operations, the battery's second working discharge capacity 31.7

[0042] In other implementations of this embodiment, the battery to which the polarity reversal and subsequent charging or charge-discharging operation method of the present invention are implemented can also be a tubular lead-acid battery, a wound lead-acid battery, a bipolar lead-acid battery, a horizontal lead-cloth lead-acid battery, a foam grid lead-acid battery, a valve-regulated sealed lead-acid battery, a colloidal lead-acid battery, a lead-carbon battery, a supercapacitor-lead-acid battery, a columnar lead-acid battery, or a lead-acid battery with a stable void electrode; the polarity reversal and subsequent charging or charge-discharging operation of the present invention can also be started when the remaining capacity of the battery is 50%, 90%, or 100% of the rated capacity; the voltage when the battery stops working is not only 2.65V, but can also be Any other possible voltage, such as 2.8V, 2V, 1.75V, 0.5V, 0V; when the battery is stopped, the battery can also be in other stages of operation, such as constant current discharge stage or constant current charging stage; the basis for starting or stopping the polarity reversal of the present invention and the subsequent charging or charge-discharge operation can also be other physical values ​​or / and chemical values ​​or / and quantity values, including voltage value, current value, current density value, electric quantity value, power value, time value, temperature value, force value, pressure value, density value, luminosity value, frequency value, cumulative value, odd value, even value, ratio value, charging or discharging or charge-discharge cycle number value of the battery or / and battery pack, acidity value of the battery or / and battery pack One or more.

[0043] In other implementations of this embodiment, the discharge current in step 1) is a current with an absolute value greater than 0, such as a current of 0.01, 0.1, 1, 3, 5, and 10 times the rate; the discharge can also be carried out in stages and the discharge current value in each stage is not necessarily the same; the voltage at which the discharge stops can be 0V, or other voltages, such as 0.5, 0.2, -0.3, -1.7V, -2.33, -2.8V, etc.; a charging stage can also be added, that is, after discharging for a certain period of time, the battery is charged for more than one stage, and then discharged after charging. The number of cycles of discharge, charging, discharging, etc. is unlimited, and the polarity is reversed after the charge and discharge cycle.

[0044] In other implementations of this embodiment, the basis for the termination of the charging or charging and discharging operation in step 1) is not necessarily the voltage, but can also be other physical quantities or / and chemical quantities or / and quantity values, including voltage value, current value, current density value, charge value, power value, time value, temperature value, force value, pressure value, density value, luminosity value, frequency value, cumulative value, odd value, even value, ratio value, charging or discharging or charge and discharge cycle number value of the battery or / and battery pack, acidity value of the battery or / and battery pack or one or more thereof.

[0045] In other implementations of this embodiment, the discharge step in step 1) can be omitted, that is, after stopping the operation of the battery, step 2) is directly performed.

[0046] In other implementations of this embodiment, the connection transformation in step 2) and step 5) may also be achieved through automatic functions of equipment, devices or circuits instead of manual operations.

[0047] In other implementations of this embodiment, the charging current in step 3) is a current with an absolute value greater than 0, such as a current of 0.01, 0.2, 1.1, 3.5, 5.3, and 10 times; charging can also be performed in stages and the charging current value in each stage is not necessarily the same; the voltage at which charging is stopped is not necessarily 1.75V, but can be other voltages, such as; 0.3, 0.5, 1.0, 2.0, 2.44, 2.65, 2.8V, etc.; the basis for stopping charging can also be the charging amount and time;

[0048] In other implementations of this embodiment, the discharge current in step 4) is a current with an absolute value greater than 0, such as currents of 0.01, 0.1, 1, 3, 5, and 10.3 times; the discharge can also be carried out in stages and the discharge current value in each stage is not necessarily the same; the discharge stage can also be added with a charging stage, that is, after discharging for a certain period of time, the battery is charged for one stage or more, and then discharged after charging. The number of cycles of discharge, charge, discharge, etc. is unlimited, and the polarity is reversed after the charge and discharge cycle.

[0049] In other implementations of this embodiment, the discharge operation in step 4) may not be performed, and the process may directly proceed to step 5) after the charging in step 3) is completed.

[0050] In other implementations of this embodiment, the basis for the termination of the charging or charge-discharging operation in step 3 or step 4) is not necessarily the voltage, but can also be other physical quantities or / and chemical quantities or / and quantity values, including voltage value, current value, current density value, charge value, capacity value, power value, time value, temperature value, force value, pressure value, density value, luminosity value, frequency value, cumulative value, odd value, even value, ratio value, battery or / and battery pack charge or discharge or charge and discharge cycle number value, battery or / and battery pack acidity value or more.

[0051] In other implementation modes of this embodiment, the charging current in step 6) is a current with an absolute value greater than 0, such as a current of 0.01, 0.1, 1, 3, 5, or 10 times the rate; charging can also be performed in stages and the charging current value in each stage is not necessarily the same; the voltage at which charging stops is not necessarily 1.75V, but can be other voltages, such as; 0.3, 0.5, 1.0, 2.0, 2.4, 2.65, 2.78V, etc.; a discharging stage can also be added to the charging stage, that is, after charging for a certain period of time, the battery is discharged for more than one stage, and then charged after discharging. The number of cycles of charging, discharging, charging, discharging, etc. is unlimited. After the charge and discharge cycle, the battery is transferred to a working state or a quasi-working state.

[0052] In other implementations of this embodiment, after completing the operation of step 6), continue the operation of steps 1)-6) for more than one time (i.e., the operation of steps 1) to 6), and then perform the battery operation for more than one time, and the operation of steps 1)-6) for more than one time and the battery operation for more than one time can be performed alternately and cyclically, and the number of cycles is ≥ 1. In this way, the original positive electrode of the battery always works as the positive electrode, and the original negative electrode always works as the negative electrode.

[0053] In other implementations of this embodiment, after completing the operation of step 6), continue to perform the operation of steps 1)-3) once or more than one time of the operation of steps 1)-6) plus one time of the operation of steps 1)-3), and then perform the battery operation once more, and the operation of steps 1)-3) once or more than one time of the operation of steps 1)-6) plus one time of the operation of steps 1)-3) and the battery operation once more can be performed alternately and cyclically, and the number of cycles is ≥ 1. In this way, the original positive electrode of the battery always works as the negative electrode, and the original negative electrode always works as the positive electrode.

[0054] In other implementations of this embodiment, after the battery completes the operation of step 6), the battery is operated more than once, the operation of steps 1)-6) is performed more than once, the operation of steps 1)-3) is performed once, or the operation of steps 1)-6) is performed more than once plus the operation of steps 1)-3) is performed alternately and cyclically. The order of rotation is not limited, and the number of cycles is ≥1. In this way, the original positive electrode of the battery sometimes works as the positive electrode and sometimes works as the negative electrode. Correspondingly, the original negative electrode of the battery sometimes works as the negative electrode and sometimes works as the positive electrode.

[0055] In other implementations of this embodiment, the basis for starting the switch between any two of the battery operation of more than one time, the operation of steps 1)-6) of more than one time, the operation of steps 1)-3) of one time, or the operation of more than one time of steps 1)-6) plus the operation of step 1)-3) of one time may be a physical value or / and a quantity value or / and a chemical value, including one or more of a voltage value, a current value, a current density value, a charge value, a power value, a time value, a temperature value, a force value, a pressure value, a density value, a luminosity value, a frequency value, a cumulative value, an odd value, an even value, a proportional value, a charge or discharge value or a charge and discharge cycle number value of a battery or / and a battery pack, and an acidity value of a battery or / and a battery pack.

[0056] In other implementations of this embodiment, one or more of the above-mentioned physical quantity values, quantitative values, chemical quantity values ​​and their change values, calculated values ​​include physical quantity values, quantitative values ​​or chemical quantity values ​​of the battery during charging, discharging, open circuit or static state.

[0057] In other implementations of this embodiment, during the operations of steps 1) to 6) above, other operations may be performed simultaneously, such as adjusting the temperature of the battery, adding acid, adding additives, adding water, and increasing pressure to the battery.

[0058] The charge and discharge current used in this embodiment is direct current. In other implementations of this embodiment, the charge and discharge current used may also be a pulse charge current or a composite current of a pulse charge current and a direct current.

[0059] In other implementations of this embodiment, in the operations of steps 1) and 4) above, the standing time may be other time lengths, and the standing time may also be 0;

[0060] In other implementations of this embodiment, the operations of steps 1) to 6) above may be performed by programming.

[0061] The above operation of this example can improve and reverse the softening and shedding of the positive active material of the lead-acid battery, and can improve, repair, enhance and restore the working discharge capacity of the lead-acid battery, thereby improving or extending the service life of the lead-acid battery.

[0062] Example 2

[0063] The lead-acid battery of the present embodiment is a flat grid lead-acid battery, with a rated capacity of 1.77Ah (2h rate, 25°C), a rated voltage of 2V, a structure with a positive plate sandwiched between two negative plates, an AGM separator between the positive and negative electrodes, a total capacity of the negative plates relatively exceeding the total capacity of the positive plates, a thickness of the positive plate of 2.8mm, a thickness of the negative plate of 1.9mm, and rectangular grids of the positive and negative plates. The positive plate has a positive lead paste formula (wherein the content of sulfuric acid relative to ball-milled lead powder is 4.5wt.%, and the formula does not contain barium sulfate) made of The positive electrode lead paste is used only as the positive electrode when the battery is working, so it is called the positive electrode plate (for the sake of clarity in the subsequent statements, it is also named electrode A in this embodiment), the negative electrode plate has a negative electrode lead paste made from the current common commercial negative electrode lead paste formula, and is only used as the negative electrode when the battery is working, so it is called the negative electrode plate (for the sake of clarity in the subsequent statements, it is also named electrode B1 and B2 in this embodiment), the lead powder used in the positive and negative electrode lead pastes is the current common commercial ball-milled lead powder, the mass of the dry lead paste on the positive electrode plate after curing and drying is 29.69g, and the density of the sulfuric acid solution in the lead-acid battery in this embodiment is 1.27g / cm 3 This embodiment eliminates or prevents factors such as fluid loss, open circuit, short circuit, mechanical damage, and test failure from interfering with the implementation process and results of this embodiment.

[0064] The method for improving or extending the service life of the lead-acid battery of the present embodiment is as follows: first, the lead-acid battery of the present embodiment is subjected to cyclic charge and discharge operation. The cyclic charge and discharge operation system of the lead-acid battery of the present embodiment is as follows: when the battery is in a charged state, the battery is discharged at a constant current of 1031 mA. When the discharge time reaches 1 hour and 36 minutes (i.e., the discharge capacity is 1649 mAh, which is 93% of the rated capacity), or the battery voltage is ≤1.75 V, the discharge is stopped, and then the battery is charged at a constant current of 412 mA. When the battery voltage reaches 2.65 V, the battery is switched to a constant voltage of 2.65 V to continue charging the battery. When the total time of two (constant current, constant voltage) charging reaches 6 hours and 24 minutes, the battery charging process is terminated. Then, the aforementioned discharge process is repeated at a constant current of 1031 mA. Discharge, charge, discharge, and charge are repeated in this way, so that the battery is cyclically charged and discharged, and the working environment temperature of the battery is 25±1° C.; secondly, when the positive active material softens or / and falls off, When the discharge capacity or discharge time of the lead-acid battery of the present embodiment is less than a certain preset capacity value or a certain time value (for example, in the present embodiment, the values ​​are set to be 900 mAh, 1 hour 36 minutes, and 47 minutes, respectively, as shown below), the battery is stopped, and the battery is subjected to at least one period of two consecutive positive and negative polarity reversals and subsequent charging or charging and discharging operations, so that after the operation is completed, the working discharge capacity of the lead-acid battery of the present embodiment is restored or improved, and then the battery is put back into its original working system to continue working; and then, in the process of cyclic charging and discharging operation (referred to as cyclic operation, the same below) of the lead-acid battery of the present embodiment, the same or similar two consecutive positive and negative polarity reversals and subsequent charging or charging and discharging operations as described above in the present embodiment are repeatedly, interspersedly, and in multiple periods, thereby inhibiting, preventing, repairing, improving, eliminating, or reversing the softening and / or shedding of the positive active material of the lead-acid battery, and significantly improving or extending the service life of the lead-acid battery of the present embodiment.Specifically, through the battery charger and discharger of this embodiment and its setting program and execution function, the polarity reversal of the positive plate and the negative plate of the lead-acid battery of this embodiment and the subsequent charging or charging and discharging operation are set and executed. When performing the polarity reversal operation of the positive plate and the negative plate of the lead-acid battery of this embodiment, one is manual operation: the battery voltage is reduced to near 0V, and then the connection state of the battery charger and discharger of this embodiment and the lead-acid battery of this embodiment is changed by hand from the positive electrode clip of the charger and discharger (positive electrode output conductive clip, the same below) connected to the positive plate (electrode A) of the lead-acid battery, and the negative electrode clip of the charger and discharger (negative electrode output conductive clip, the same below) connected to the negative plate (electrodes B1, B2) of the lead-acid battery (this connection is called the positive connection state, the same below), to the positive electrode clip of the charger and discharger connected to the negative plate (electrode B1) of the lead-acid battery. , B2) connection, the negative electrode clamp of the charger and discharger is connected to the positive plate (electrode A) of the lead-acid battery (this connection is called reverse connection state, the same below), or the reverse connection state is changed to the forward connection state, and then the battery after the electrode connection state is changed is charged to the battery voltage>0V, thereby realizing the polarity reversal of the electrode of the battery of this embodiment; the other is automatic operation through the battery charger and discharger of this embodiment: when the lead-acid battery of this embodiment is in the forward connection state, the constant current source in the battery charger and discharger of this embodiment is used to force the battery of this embodiment to discharge so that the battery voltage changes from a state of ≥0V to a state of <0V, or when the battery voltage is <0V, the battery is charged (or forced charging) and the battery voltage changes from a state of <0V to a state of ≥0V, that is, the polarity reversal operation of the lead-acid battery of this embodiment is automatically realized. When the battery is in the positive connection state, the battery is forced to continue to discharge when the battery voltage is less than 0V, so that the battery voltage tends to be more negative. At this time, the main process occurring on the positive plate (electrode A) of the battery is the charging process in the negative electrode reaction of the lead-acid battery, and the main process occurring on the negative plate (electrodes B1, B2) of the battery is the charging process in the positive electrode reaction of the lead-acid battery (refer to the electrode reaction formulas (1) and (2) of the present invention, the same below). When the battery of the present embodiment is in the positive connection state, the battery is forced to charge when the battery voltage is less than 0V, so that the battery voltage tends to be more positive or 0V. At this time, What mainly occurs on the positive plate (electrode A) of the battery is the discharge process in the negative electrode reaction of the lead-acid battery, and what mainly occurs on the negative plate (electrodes B1, B2) of the battery is the discharge process in the positive electrode reaction of the lead-acid battery; when the battery of this embodiment is in a positive connection state, the battery is charged when the battery voltage is greater than 0V, so that the battery voltage tends to be more positive, then at this time, what mainly occurs on the positive plate (electrode A) of the battery is the charging process in the positive electrode reaction of the lead-acid battery, and what mainly occurs on the negative plate (electrodes B1, B2) of the battery is the charging process in the negative electrode reaction of the lead-acid battery.In this way, the forced discharge and forced charging functions and operations of the battery charger and discharger of this embodiment realize the polarity reversal operation of the positive and negative poles of the battery of this embodiment, as well as the charging or charging and discharging operation after the polarity reversal. In addition, the charging and discharging functions of the battery charger and discharger of this embodiment are also used to implement the charging and discharging operations of the lead-acid storage battery of this embodiment during operation, so as to realize the cyclic charging and discharging operation of the battery of this embodiment (all operations and measurements of the lead-acid storage battery of this embodiment are set by the battery charger and discharger of this embodiment, except for those that are specially stated to be manual). The specific implementation process of the method for improving or extending the service life of the lead-acid storage battery of this embodiment is as follows:

[0065] According to the above, it is initially set that when the working discharge capacity of the lead-acid storage battery of this embodiment is less than 900mAh, the lead-acid storage battery of this embodiment is stopped and the first and second positive and negative polarity reversals and subsequent charging or charging and discharging operations are performed on the battery. The battery of this embodiment starts to perform charging and discharging cycle work according to the working system of this embodiment from the second charging and discharging working cycle after the formation is completed. During operation, the positive electrode reaction of the lead-acid storage battery occurs on the positive plate of the battery of this embodiment, and the negative electrode reaction of the lead-acid storage battery occurs on the negative plate, such as Figure 1As shown, when the working charge and discharge cycle reaches the 148th time, the working discharge capacity of the battery of this embodiment begins to show a phenomenon of gradual decrease. After inspection, this is caused by the softening and shedding of the positive electrode active material (the reasons for the decrease in the working discharge capacity are the same below). When the charge and discharge cycle works to the 179th time, the working discharge capacity of the battery when discharged to 1.75V drops to 899mAh (that is, the remaining capacity is 50.9% of the rated capacity), that is, the triggering condition for starting the positive and negative polarity reversal and the subsequent charging or charging and discharging operation of the battery of this embodiment is reached (discharge capacity <900mAh). At this time, the preparation and formal operation of the first and second positive and negative polarity reversal and the subsequent charging or charging and discharging operation of the battery of this embodiment are started, that is, after the 179th working discharge is completed (the battery voltage is 1.75V at this time), the battery continues to be discharged at a constant current of 1031mA for 4min and stops discharging when the battery voltage is 0V, and then the polarity of the positive plate and the negative plate of the battery is reversed, that is, the battery of this embodiment is manually charged and discharged. The connection state between the charger and the lead-acid battery of this embodiment is changed from the positive connection state in which the positive electrode clamp of the charger and the positive plate (electrode A) of the lead-acid battery is connected, and the negative electrode clamp of the charger and the negative plate (electrodes B1, B2) of the lead-acid battery is connected, to the reverse connection state in which the positive electrode clamp of the charger and the negative plate (electrode B1, B2) of the lead-acid battery is connected, and the negative electrode clamp of the charger and the positive plate (electrode A) of the lead-acid battery is connected, forming the so-called reverse connection, and then the battery after the connection state is changed is charged with a constant current of 1031mA. The battery is charged in such a way that the positive plate (electrode A) of the lead-acid battery in this embodiment generates a negative electrode reaction of the lead-acid battery, and the negative plate (electrodes B1, B2) of the lead-acid battery in this embodiment generates a positive electrode reaction of the lead-acid battery. After 3 hours and 15 minutes, when the battery voltage rises to 1.75V (at this time, the negative plate or electrodes B1, B2 are positive and the positive plate or electrode A is negative), the battery is charged at a constant current of 1031mA for 3 hours (during this process, the battery voltage rises from 1.75V to 2.23V, at this time, the negative plate or electrodes B1, B2 are still positive, and the positive plate or electrode A is negative), then, the battery is discharged at a constant current of 1031mA, so that the discharge process of the negative electrode reaction of the lead-acid battery occurs on the positive plate (electrode A) of the lead-acid battery in this embodiment, and the discharge process of the positive electrode reaction of the lead-acid battery occurs on the negative plate (electrode B1, B2) of the lead-acid battery in this embodiment, and the discharge is stopped when the discharge reaches 0V after 24min, and then, the positive and negative polarities of the battery are reversed again, that is, the connection state of the battery charger and discharger with the lead-acid battery in this embodiment is manually changed from the reverse connection state in which the positive electrode clip of the charger and discharger is connected to the negative plate (electrode B1, B2) of the lead-acid battery and the negative electrode clip of the charger and discharger is connected to the positive plate (electrode A) of the lead-acid battery to the positive electrode clip of the charger and discharger connected to the negative plate (electrode The battery is charged at a constant current of 258.4 mA, so that the positive electrode reaction of the lead-acid battery occurs on the positive plate (electrode A) of the lead-acid battery in this embodiment, and the negative electrode reaction of the lead-acid battery occurs on the negative plate (electrodes B1, B2) of the lead-acid battery in this embodiment. The charging is carried out for 31 minutes until the battery voltage reaches 1.75 V (at this time, the positive plate or electrode A is positive, and the negative plate or electrodes B1, B2 are negative). Then, the battery is charged at a constant current of 412 mA for 16 hours and 35 minutes until the battery voltage reaches 2.65 V. Then, the battery is charged at a constant voltage of 2.65 V for 3 hours (in this constant current and constant voltage charging process, the positive plate or electrode A is positive, and the negative plate or electrodes B1, B2 are negative). After the constant voltage charging is completed, the first and second positive and negative polarity reversals of the battery in this embodiment and the subsequent charging or charge-discharging operations are completed. Then, the battery was put back into the same charge and discharge cycle working state and system for the 180th working discharge and subsequent cyclic charge and discharge work. The results showed that after the first and second positive and negative polarity reversal and the subsequent charging or charge and discharge operation, the discharge capacity of the battery in the 180th working state increased to 1452.5mAh, and its discharge capacity in the 181st working state had recovered to the normal discharge capacity of 1649mAh (corresponding to a discharge time of 1 hour and 36 minutes).

[0066] Next, the battery of this embodiment continues to operate under the working system, and the conditions for triggering the positive and negative polarity reversal and the subsequent charging or charge-discharging operation are changed through programming to: when the working discharge time of the lead-acid storage battery of this embodiment is less than 1 hour and 36 minutes, the battery operation is stopped and the third and fourth positive and negative polarity reversals and the subsequent charging or charge-discharging operations are automatically started. Figure 1As shown, the working discharge capacity in the 181st-224th discharge-charge working cycle all reaches the normal discharge time, 1 hour and 36 minutes (the corresponding discharge capacity is 1649mAh). During the cyclic charge-discharge working process, the positive electrode reaction of the lead-acid battery occurs on the positive plate (electrode A) of the battery of this embodiment, and the negative electrode reaction of the lead-acid battery occurs on the negative plate (electrodes B1, B2). When the battery charge-discharge cycle works to the 225th time, the discharge working capacity of the battery begins to decrease. When the discharge time is 1 hour and 35 minutes (at this time, the battery discharge termination voltage has dropped to 1.75V), therefore, according to the set trigger conditions and execution procedures, the battery charger and discharger of this embodiment immediately discharges the battery of this embodiment. The battery automatically switches from the working state to the preparation and implementation stage of the polarity reversal of the positive plate and the negative plate and the subsequent charging or charging and discharging operation, that is, after the 225th charging and discharging cycle is completed and the battery voltage drops to 1.75V, the battery is stopped working, so that the connection state between the battery and the charger and discharger is in the positive connection state, that is: the positive electrode of the output end of the battery charger and discharger of this embodiment is connected to the positive plate (electrode A) of the lead-acid battery of this embodiment, and the negative electrode of the output end of the battery charger and discharger of this embodiment is connected to the negative plate (electrodes B1, B2) of the lead-acid battery of this embodiment, and then the battery of this embodiment is automatically discharged and forcedly discharged at a constant current of 1031mA, and the forced discharge of the battery charger and discharger of this embodiment is performed. The battery voltage of the present embodiment is reduced from 1.75V to 0V quickly after 23min of continuous discharge and forced discharge operation (this process causes the positive electrode reaction of the lead-acid battery to occur on the positive plate or electrode A of the lead-acid battery of the present embodiment, and the negative electrode reaction of the lead-acid battery to occur on the negative plate or electrodes B1, B2 of the lead-acid battery of the present embodiment). Then, the battery voltage is reduced from 0V to -1.75V after 36min (the battery voltage measured and displayed by the battery charger and discharger, the same below, this process causes the negative electrode reaction of the lead-acid battery to occur on the positive plate or electrode A of the lead-acid battery of the present embodiment, and the charging process of the lead-acid battery to occur on the negative plate or electrodes B1, B2 of the lead-acid battery of the present embodiment). After reaching -1.75V, the battery is forced to discharge at a constant current of 1031mA for 3 hours (the battery voltage is measured to drop from -1.75V to about -2.15V during this process, and the charging process of the negative electrode reaction of the lead-acid battery occurs on the positive plate (electrode A) of the lead-acid battery in this embodiment, and the charging process of the positive electrode reaction of the lead-acid battery occurs on the negative plate (electrode B1, B2) of the lead-acid battery in this embodiment). Then, the charger and discharger forcefully charges the battery at a constant current of 1031mA (it is measured that the charging process takes 23 minutes, and the battery voltage drops from about -2.The voltage of the battery rises from 15V to 0V (this process causes the discharge process of the lead-acid battery negative electrode reaction to occur on the positive plate or electrode A of the lead-acid battery in this embodiment, and the discharge process of the lead-acid battery positive electrode reaction to occur on the negative plate or electrodes B1, B2 of the lead-acid battery in this embodiment). When the battery voltage reaches 0V, the charger and discharger automatically continue to charge the battery at a constant current of 258.4mA. After 1 hour and 8 minutes, the battery voltage reaches 1.75V (this process causes the charging process of the lead-acid battery positive electrode reaction to occur on the positive plate or electrode A of the lead-acid battery in this embodiment, and the charging process of the lead-acid battery negative electrode reaction to occur on the negative plate or electrodes B1, B2 of the lead-acid battery in this embodiment). The battery is charged at a constant current of 412 mA for 8 hours and 41 minutes, and the measured battery voltage reaches 2.65V. Then, the battery is charged at a constant voltage of 2.65V, and the constant voltage charging is maintained for 3 hours (the positive plate or electrode A is positive, and the negative plate or electrode B1 and B2 are negative during this constant current and constant voltage charging process). After the constant voltage charging is completed, the third and fourth positive and negative polarity reversals and subsequent charging or charging and discharging operations of the battery of this embodiment are completed, and then the battery of this embodiment is returned to its original, same cycle charging and discharging working state and system for the 226th and subsequent cycle charging and discharging operations. The results show that after the third and fourth positive and negative polarity reversals and subsequent charging or charging and discharging operations, the discharge time of the battery of this embodiment in the 228th cycle operation is restored to 1 hour and 36 minutes, and its working discharge time is normal from the next cycle operation to the 239th cycle operation, which is 1 hour and 36 minutes. (Due to misoperation, the discharge termination voltage of the 226th and 227th working cycles was lower than 1.75V, resulting in over-discharge).

[0067] Next, the battery of this embodiment is allowed to continue to operate under the working system, such as Figure 1As shown, when the battery of this embodiment is cycled to the 240th time, its discharge time is 1 hour and 35 minutes, the previously set positive and negative polarity reversal and the subsequent charging or charge-discharging operation start conditions are triggered again. Therefore, after the 240th discharge operation is completed (the battery voltage is 1.75V at the end of the discharge), the charger and discharger then starts the fifth and sixth polarity reversal of the positive and negative plates of the battery of this embodiment and the subsequent charging or charge-discharging operations. The operation method and process are the same as the third and fourth positive and negative polarity reversal and the subsequent charging or charge-discharging operations of this embodiment. Then, the lead-acid storage battery of this embodiment re-enters the same cyclic charge and discharge working state and system and then performs the 241st and subsequent cyclic charge and discharge operations of the battery of this embodiment. As a result, after the fifth and sixth reversal of the positive and negative polarity and subsequent charging or charge-discharging operations, the discharge time of the battery in this embodiment recovered to 1 hour and 36 minutes in the 243rd cycle (the 241st and 242nd working cycles resulted in over-discharge due to misoperation resulting in the discharge termination voltage being lower than 1.75V).

[0068] Next, the battery of this embodiment continues to operate under the working system, and during the 244th charge-discharge cycle, the starting conditions for triggering the reversal of the positive and negative polarities of the battery of this embodiment and the subsequent charging or charging and discharging operations are changed through programming to: when the discharge time of the battery of this embodiment is less than 45 minutes, the battery operation is stopped and the seventh and eighth reversals of the positive and negative polarities of the lead-acid storage battery of this embodiment or its positive and negative plates and the subsequent charging or charging and discharging operations are automatically performed. Figure 1As shown in the figure, when the battery of this embodiment works for the 251st cycle, its discharge performance begins to decline. At the 268th cycle, the working discharge time is 42 minutes (corresponding to the working discharge capacity of 721 mAh), at which time the set positive and negative polarity reversal and the subsequent charging or charge-discharge operation start conditions are triggered. Therefore, after the 268th discharge operation is completed (the battery voltage is 1.75 V at the end of the discharge), the battery operation is stopped, and the charger and discharger then starts to perform the seventh and eighth polarity reversals of the positive and negative plates and the subsequent charging or charge-discharge operations on the battery of this embodiment. The operation method and process are the same as those of the third and the fourth cycles of this embodiment. The four reversals of the positive and negative polarity and the subsequent charging or charge-discharging operations are basically the same, except that after the battery voltage reaches -1.75V, the constant current of 1031mA is maintained for forced discharge for 4 hours (instead of 3 hours, and the battery voltage measured in this process still drops from -1.75V to about -2.15V). After the seventh and eighth reversals of the polarity of the positive and negative plates and the subsequent charging or charge-discharging operations are completed, the lead-acid battery of this embodiment re-enters the same cyclic charge-discharging working state and system and then performs the 269th and subsequent cyclic charge-discharging operations of the battery of this embodiment. As a result, after the seventh and eighth reversal of the positive and negative polarity and the subsequent charging or charge-discharge operations, the discharge time of the battery in this embodiment recovered to 1 hour and 12 minutes (discharge capacity is 1252 mAh) in the 269th cycle operation, and the discharge time recovered to 1 hour and 36 minutes in the 270th cycle operation, and its working discharge time was a normal 1 hour and 36 minutes in the subsequent cycle charge and discharge operations until the 290th cycle.

[0069] like Figure 1As shown, in the next 270th to 463rd cycle operation of the lead-acid storage battery of this embodiment, its cyclic charge and discharge working state and system are the same as those of the 1st to 270th cycle operation, and whenever the working discharge time or working discharge capacity of the lead-acid storage battery of this embodiment drops to 1 hour and 36 minutes or 1649 mAh or less, the lead-acid storage battery of this embodiment is subjected to a period of polarity reversal and subsequent charging or charging and discharging operations similar to the above two consecutive polarity reversals, that is, between the 295th and 296th cycles, between the 309th and 310th cycles, between the 324th and 325th cycles, between the 344th and 345th cycles, between the 369th and 370th cycles, between the 385th and 390th cycles, and between the 391st and 393rd cycles. Between the 86th time, the 405th and 406th time, the 425th and 426th time, the 441st and 442nd time, and the 457th and 458th time, the ninth and tenth time, the eleventh and twelfth time, ..., the twenty-seventh and twenty-eighth time, a total of 10 periods of polarity reversal and subsequent charging or charge-discharging operations were performed respectively, and the working discharge time or capacity of the lead-acid battery of this embodiment was restored to 1 hour 36 minutes or 1649 mAh in the first or second working discharge after two consecutive polarity reversals and subsequent charging or charge-discharging operations in each period, so that the lead-acid battery of this embodiment retains the ability to continue normal working discharge.

[0070] like Figure 1As shown, after two consecutive polarity reversals and subsequent charging or charge-discharging operations in each period in this embodiment, the working discharge time or capacity of the lead-acid battery in this embodiment is restored to 1 hour and 36 minutes or 1649 mAh in the first or second working discharge after the operation. This may be related to the degree of decrease in the actual working discharge capacity of the battery before the start of each polarity reversal operation, the size and method of the current, voltage, charge-discharge capacity, number of stages, etc. during each polarity reversal and subsequent charging or charge-discharging operation. For example, if the active material particles on the positive plate are softened or fall off to a large extent, or the actual working discharge capacity of the battery decreases to a large extent, when performing two consecutive polarity reversals and subsequent charging or charge-discharging operations in a period, the demand for charging after the first polarity reversal in this period is also relatively large, and a large charging amount after the second polarity reversal in this period is beneficial to ensuring that the battery is fully charged. Therefore, if the charging amount after the second polarity reversal in this period is relatively small, it may cause the battery to be undercharged, which will require the lead-acid battery of this embodiment to continue to replenish the battery charge through the first working discharge and charging process after two consecutive polarity reversals and subsequent charging or charge-discharging operations.For example, the two consecutive polarity reversals and the subsequent charging or charging and discharging operations performed between the 405th and 406th times or between the 441st and 442nd times of the working discharge of the lead-acid battery of this embodiment, it can be seen from the 405th or 441st working discharge results that the degree of decrease in the working discharge capacity of the lead-acid battery of this embodiment is less than that of the 179th time. The two consecutive polarity reversals and the subsequent charging or charging and discharging operations performed between the 405th and 406th times are as follows: after the 405th working discharge (at this time, the battery voltage is 1.75V), while keeping the battery charger and discharger in a positive connection state with the battery of this embodiment, continue to discharge and force discharge the battery at a constant current of 1031mA for 132min, so that the battery voltage increases from 1 .75V drops to 0V, and then drops from 0V to -1.75V (wherein, in the process of dropping from 1.75V to 0V, the positive plate or electrode A mainly undergoes the discharge process of the positive electrode reaction of the lead-acid battery, and the negative plate or electrodes B1 and B2 mainly undergoes the discharge process of the negative electrode reaction of the lead-acid battery. In the process of dropping from 0V to -1.75V, the positive plate or electrode A mainly undergoes the charging process of the negative electrode reaction of the lead-acid battery, and the negative plate or electrodes B1 and B2 mainly undergoes the charging process of the positive electrode reaction of the lead-acid battery). When it reaches -1.75V, the polarity of the negative plate (electrodes B1 and B2) is positive and the polarity of the positive plate (electrode A) is negative. Then, continue to charge at 1031mA The battery was forced to discharge at a constant current of 1031 mA for 4 hours (during this process, the battery voltage continued to drop from -1.75 V to -2.087 V, at this time, the negative plate or electrodes B1 and B2 were still positive and the positive plate or electrode A was negative), and then the battery was forced to charge at a constant current of 1031 mA, so that the discharge process of the lead-acid battery negative electrode reaction occurred on the positive plate (electrode A) of the lead-acid battery in this embodiment, and the discharge process of the lead-acid battery positive electrode reaction occurred on the negative plate (electrode B1 and B2) of the lead-acid battery in this embodiment. The forced charging was stopped when the voltage reached 0 V for 35 minutes, and then the battery was charged at a constant current of 258.4 mA again, so that the lead-acid battery positive plate (electrode A) of the lead-acid battery in this embodiment occurred. The charging process of the positive electrode reaction of the lead-acid battery, the charging process of the negative electrode reaction of the lead-acid battery occurring on the negative plate (electrodes B1, B2) of the lead-acid battery of the present embodiment, the charging is carried out for 1 hour and 21 minutes, to when the battery voltage reaches 1.75V (at this time, the positive plate or electrode A is positive, and the negative plate or electrodes B1, B2 are negative), and then charged at a constant current of 412mA for 14 hours, to a battery voltage of 2.63V, and then, the battery is charged at a constant voltage of 2.65V for 4 hours (in this constant current and constant voltage charging process, the positive plate or electrode A is positive, and the negative plate or electrodes B1, B2 are negative), and then, the battery is re-entered into the same cyclic charge and discharge working state and system to carry out the 406th working discharge and subsequent number of cyclic work.The two consecutive polarity reversals and the subsequent charging or charge-discharging operations between the 441st and 442nd times are basically the same as those between the 405th and 406th times, except that, in the two consecutive polarity reversals and the subsequent charging or charge-discharging operations between the 441st and 442nd times, the forced discharge current after the first polarity reversal is 1515mA (that is, the forced discharge causes the negative electrode reaction of the lead-acid battery to occur on the positive plate or electrode A during the charging process, and causes the positive electrode reaction of the lead-acid battery to occur on the negative plate or electrodes B1, B2 during the charging process).

[0071] In this embodiment, if the working discharge capacity is defined as less than 80% of the rated capacity, it is considered as invalid work or not counted in the number of cycle charge and discharge operations (i.e., battery life), then before the lead-acid battery of this embodiment is subjected to the first phase or the first polarity reversal of this embodiment and the subsequent charging or charging and discharging operation, if Figure 1 As shown, the effective working cycle number or service life is 145 cycles (after 143 cycles, the working discharge capacity is less than 80% of the rated capacity for three consecutive times). However, through the positive and negative polarity reversal and the subsequent charging or charging and discharging operation method, lead-acid battery, and battery charger and discharger of this embodiment, the lead-acid battery of this embodiment can continue to work normally after 463 cycles, and the effective working cycle number reaches 408 times, which is increased by 181%. It can be inferred from the above that the service life of the lead-acid battery of this embodiment can be further extended by continuing to follow the above operation method without generating collector corrosion, water loss, etc.

[0072] In addition, if the cost and benefit evaluation is performed by taking the first 8 polarity reversals and the subsequent charging or charge-discharging operations of the present embodiment as an example, the total additional charge consumed by the first 8 positive and negative polarity reversals and the subsequent charging or charge-discharging operations of the battery in the present embodiment is about 47336 mAh, and the additional effective working times are 83 times. Therefore, the average additional charge consumed for each additional working time is 570 mAh, which is 34.6% of the rated capacity of the lead-acid battery in the present embodiment. Combined with the current commercial power lead-acid battery, it is calculated that the cost of increasing each effective work is about 0.036% of the purchase cost of the current commercial power lead-acid battery (the electricity fee is calculated at 0.6 yuan / kWh), and the cost of increasing 365 effective works is about 13.2% of the purchase cost of the current commercial power lead-acid battery. That is, if the cost of the charger and discharger of the present embodiment is not taken into account, the method of improving or extending the service life of the lead-acid battery in the present embodiment can reduce the use cost of the power battery to 13.2% in one year. If the working discharge system is relatively mild (the discharge depth and discharge current are less than 93% DOD and 1.16I2 in this example, where I2 is 0.5 times the rate current), the additional charge consumed for each additional working time is even lower, so the cost of each effective working time is also correspondingly lower. In addition, the environmental benefits brought by each additional year of battery life are huge. In addition, the polarity reversal and subsequent charging or charge-discharge operation of this embodiment adopts a pulse charging method to perform polarity reversal and subsequent charging or charge-discharge, which will further improve the efficiency of the operation, reduce the cost of the operation, and improve the benefits of the operation.

[0073] As described above, the reversal of the positive and negative polarities of the present embodiment and the subsequent charge and discharge or charge and discharge operation improves, repairs, and reverses the softening and shedding of the positive active material of the lead-acid battery of the present embodiment, thereby improving or restoring the working discharge capacity of the lead-acid battery of the present embodiment during the cycle operation, thereby improving or extending the service life of the lead-acid battery of the present embodiment.

[0074] In other implementations of the present embodiment, the lead-acid battery of the present embodiment has an identity identification system, through which the battery identity identification system, the battery charger and discharger of the present embodiment can identify the battery of the present embodiment, thereby determining the entire or recent working history of the battery of the present embodiment, various related program settings, etc., so that after the battery charger and discharger of the present embodiment is connected to the battery of the present embodiment, the positive and negative polarities of the battery of the present embodiment are reversed and then charged or charged and discharged.

[0075] In other implementations of this embodiment, the forced discharge time after the lead-acid battery of this embodiment is forced to discharge to a battery voltage of less than 0V or -1.75V can also be 5 hours, 10 hours, or 20 hours, so that the battery voltage can reach -2.3V, -2.65V, -2.78V, etc., to obtain a stronger softening and shedding reversal effect of the positive electrode active material.

[0076] In other implementations of this embodiment, when the measured concentration of the electrolyte in the battery is higher than 55% and the battery temperature is higher than 45°C, the reversal of the positive and negative polarity and the subsequent charging or charge-discharging operation are suspended, and when the concentration of the electrolyte is lower than 50% (which can be achieved by replenishing the battery) and the temperature drops to less than 40°C, the reversal of the positive and negative polarity and the subsequent charging or charge-discharging operation are started.

[0077] In other implementations of this embodiment, when the battery of this embodiment is working, the positive and negative polarity are reversed, and the subsequent charging or charge-discharging operation is carried out or stopped, the battery of this embodiment is replenished with liquid, and the replenished liquid includes one or more of water, sulfuric acid solution, and additive solution to repair the battery loss of water, acid, additives, etc. caused by long-term, multiple, high-current charging and discharging, overcharging, oxidation, battery sealing problems, etc., thereby improving the battery life.

[0078] In other implementations of this embodiment, the method of improving or extending the service life of a lead-acid battery in this embodiment is applied to the lead-acid battery pack in this embodiment. The rated voltage of the lead-acid battery pack in this embodiment is 12V and the rated capacity is 12Ah. In the implementation of the method, corresponding changes are mainly made to the setting and execution of the numerical values ​​of voltage, current, capacity, etc. in the operation. For example, after the lead-acid battery pack is forced to discharge until the battery pack voltage is less than 0V, the battery pack voltage continues to drop to -6V, -10.5V, -13V, and -15V before the forced discharge is stopped. The forced discharge current is 0.3 times, 0.5 times, 1 times, and 2 times.

[0079] Example 3

[0080] The rated voltage of the lead-acid battery of the present embodiment is 2V, and the designed rated capacity is 821mAh (2h rate, 25°C). The lead-acid battery of the present embodiment includes two planar grid electrodes, and the two electrodes are both common positive and negative electrodes (i.e., electrodes common to the positive and negative electrodes), and are also the same kind of common positive and negative electrodes, that is, without considering the manufacturing error generated when manufacturing the electrodes, the two electrodes of the lead-acid battery of the present embodiment are completely identical to each other in all electrode structures and manufacturing aspects (such as electrode structure, shape, current collector, lead paste formula and lead paste quality, manufacturing process, etc.) before being formed. After being formed, the two electrodes The electrodes are formed into a positive electrode and a negative electrode respectively, and the two electrodes are defined as electrode A and electrode B respectively. At the beginning, electrode A is used as the positive electrode and electrode B is used as the negative electrode for battery formation and operation. An AGM separator is separated between the two electrodes. The current collectors of the two electrodes in this embodiment are the same as those in Example 11 of the present invention. The lead paste formula includes ball-milled lead powder, BaSO4 (0.8%, mass percentage, relative to the ball-milled lead powder), sulfuric acid, water, and short fibers. The average mass of active material on each electrode is 13.41 g. The density of the sulfuric acid solution in the lead-acid battery in this embodiment is 1.27 g / cm 3 This embodiment eliminates or prevents factors such as fluid loss, open circuit, short circuit, mechanical damage, and test failure from interfering with the implementation process and results of this embodiment.

[0081] The method for improving or extending the service life of the lead-acid battery in this embodiment is as follows: first, the battery in this embodiment is subjected to cyclic charge and discharge operation, and the working system is as follows: when the battery is in a charged state, the battery is discharged at a constant current of 371 mA, and when the battery voltage is ≤1.75 V, the discharge is stopped, and then the battery is charged at a constant current of 222 mA, and when the battery voltage reaches 2.65 V, the battery is charged at a constant voltage of 2.65 V. The total time for the two (constant current, constant voltage) chargings is 7 hours and 24 minutes (unless otherwise specified), and then the aforementioned discharge process is repeated at a constant current of 371 mA. The discharge and charging are repeated in this way to make the battery work in a cyclic manner, and the working environment temperature of the battery is 25±1°C. Secondly, when the number of working cycles of the lead-acid storage battery of this embodiment reaches a certain set value in the above-mentioned cyclic operation (for example, the set number in this embodiment is the 15th, 31st, ...), the battery stops working, and a single positive and negative polarity reversal and subsequent charging or charge-discharging operation is started on the battery. After the operation is completed, the battery continues to work under the original working system, and the positive electrode of the battery before the polarity reversal works as the negative electrode after the polarity reversal, and the negative electrode of the battery before the polarity reversal works as the positive electrode after the polarity reversal, until the next single positive and negative polarity reversal and subsequent charging or charge-discharging operation is triggered or started. In this way, during the cyclic operation of the lead-acid battery of this embodiment, the lead-acid battery of this embodiment is subjected to a single reversal of the positive and negative polarities and the subsequent charging or charging and discharging operation, so that the electrode A of the lead-acid battery of this embodiment sometimes works as the positive electrode and sometimes works as the negative electrode, and the corresponding electrode B sometimes works as the negative electrode and sometimes works as the positive electrode, so as to improve, repair, eliminate, reverse, inhibit or prevent the softening or / and shedding of the positive active material of the battery of this embodiment, so that the working discharge and charging capacity of the battery of this embodiment is improved, restored, enhanced or maintained after each operation, thereby improving or extending the service life of the lead-acid battery of this embodiment. The cyclic operation process of the battery of this embodiment is also implemented by the charging and discharging functions of the battery charger and discharger of this embodiment (all the operations and measurements of the battery below, except for those specifically stated to be manual, are all programmed and executed by the battery charger and discharger of this embodiment).

[0082] According to the above, it is initially set that when the lead-acid battery of this embodiment reaches and completes the 15th and 31st times of operation and discharge, the battery operation is stopped and the battery is started to perform a single positive and negative polarity reversal and subsequent charging or charging and discharging operation. Figure 2As shown, during the 1st to 15th cycle operation, the electrode state of the battery of this embodiment is A+ / B-, at this time, a positive electrode reaction occurs on electrode A, and a negative electrode reaction occurs on electrode B. During the 1st to 15th cycle operation, the discharge capacity of the battery of this embodiment tends to decrease overall. Upon inspection, this is mainly caused by the softening and shedding of the positive electrode active material (related to the high content of BaSO4 in the lead paste, high active material utilization rate, and deep discharge, the same below). After the 15th discharge, the discharge capacity is 942 mAh. At this time, according to the program setting, the battery charger and discharger of this embodiment automatically stops the battery operation, performs the first single positive and negative polarity reversal and the subsequent charging or charging and discharging operation preparation and formal operation, that is, after the 15th working discharge is completed (the battery voltage is 1.75V at this time), the battery operation is stopped, and the battery continues to be discharged at a constant current of 371mA for 1 hour. This process makes the battery voltage drop to 0.04V, and then the discharge is stopped, and the positive and negative polarities of the battery are reversed, that is, by reversing the polarity of the output end of the charger and discharger of this embodiment (the polarity of the output end of the charger and discharger The sex reversal is achieved by switching the open and closed states of the contacts of the relay circuit in the charger and discharger). The connection state between the charger and discharger and the lead-acid battery is changed from the positive output terminal of the charger and discharger being connected to the lead-acid battery electrode A and the negative output terminal of the charger and discharger being connected to the lead-acid battery electrode B to the negative output terminal of the charger and discharger being connected to the lead-acid battery electrode A and the positive output terminal of the charger and discharger being connected to the lead-acid battery electrode B. After the connection state is changed, the measured battery voltage is negative. Then, the battery of this embodiment after the connection state is changed is charged with a constant current of 186 mA, so that the battery voltage From a negative value to 0V and then to 1.75V (during this process, the first polarity reversal of the battery of this embodiment occurs, wherein during the process of the battery voltage rising from a negative value to 0V, the discharge process of the positive electrode reaction of the lead-acid battery occurs on electrode A, and the discharge process of the negative electrode reaction of the lead-acid battery occurs on electrode B, and during the process of the battery voltage rising from 0V to 1.75V, the charging process of the negative electrode reaction of the lead-acid battery occurs on electrode A, and the charging process of the positive electrode reaction of the lead-acid battery occurs on electrode B). When the battery voltage reaches 1.75V, continue to charge at a constant current of 222mA. The battery is charged to 2.65V with a constant current, and then charged at a constant voltage of 2.65V for 4 hours and 16 minutes, and then discharged at a constant current of 371mA to 1.75V, and then charged at a constant current of 222mA until the battery voltage reaches 2.65V, and then the battery is changed to constant voltage charging at 2.65V for 5 hours. After charging is completed, the first single positive and negative polarity reversal and subsequent charging or charge and discharge operations of the battery in this embodiment are completed. At this time, the electrode state of the battery has been changed from A+ / B- to A- / B+.Then, electrode A was operated as the negative electrode and electrode B was operated as the positive electrode, and the battery was put into the same discharge-charge cycle working system again to perform the 16th discharge and subsequent cycles. The results showed that after the first single positive and negative polarity reversal and the subsequent charging or charge-discharging operation, the discharge capacity of the battery in this embodiment in the 16th cycle working state was 888.3 mAh. The charging capacity of the battery in the process after the polarity reversal and before the battery resumed the cycle work was 7031 mAh.

[0083] Next, the battery of this embodiment is operated under the working system. Figure 2As shown, in the 16th to 31st cycle operation of the battery of this embodiment, the electrode state of the battery of this embodiment is A- / B+, at this time, a negative electrode reaction occurs on electrode A, and a positive electrode reaction occurs on electrode B. In the 16th to 31st cycle operation of the battery of this embodiment, the discharge capacity changes from 888.3mAh to 905mAh, wherein the discharge capacity increases to 987.6mAh in the 27th working cycle because the battery is overcharged once by manual intervention before this discharge (i.e., the 2.65V constant voltage charging time is 10 hours longer than that under the normal working system), and the working system of other cycle numbers remains unchanged.When the 31st cycle of discharge is completed, according to the program setting, the start conditions for the polarity reversal of the positive and negative electrodes of the battery and the subsequent charging or charging and discharging operation are triggered at this time. Therefore, the charger and discharger of this embodiment automatically starts the preparation and formal operation of the second single positive and negative polarity reversal and the subsequent charging or charging and discharging operation of the battery. That is, after the 31st cycle of discharge is completed (the battery voltage is 1.75V at this time), the charger and discharger of this embodiment stops the battery operation and continues to discharge the battery at a constant current of 371mA for 1 hour. This process causes the battery voltage to drop to 0.02V, and then stops discharging. The positive and negative polarities of the battery are reversed, that is, by reversing the polarity of the output end of the charger and discharger of this embodiment (the polarity reversal of the output end of the charger and discharger is achieved by changing the open and closed states of the contacts of the relay circuit in the charger and discharger), the connection state between the charger and discharger and the lead-acid battery is changed from the positive output end of the charger and discharger being connected to the lead-acid battery electrode B and the negative output end of the charger and discharger being connected to the lead-acid battery electrode A to the positive output end of the charger and discharger being connected to the lead-acid battery electrode A and the negative output end of the charger and discharger being connected to the lead-acid battery electrode B. After the connection state is changed, the measured battery voltage is The voltage of the battery in this embodiment is negative, and then the battery after the connection state change is charged at a constant current of 186 mA for 15 minutes, and then the battery is charged at a constant current of 371 mA, so that the battery voltage rises from a negative value to 0 V and then rises to 2.65 V (during this process, the second polarity reversal of the battery in this embodiment occurs, wherein during the process of the battery voltage rising from a negative value to 0 V, the discharge process of the negative electrode reaction of the lead-acid battery occurs on electrode A, and the discharge process of the positive electrode reaction of the lead-acid battery occurs on electrode B, and during the process of the battery voltage rising from 0 V to 2.65 V, the positive electrode reaction of the lead-acid battery occurs on electrode A. The battery is charged at a constant voltage of 2.65V for 4 hours, and then discharged to 1.75V at a constant current of 371mA. Then, the battery is charged at a constant current of 222mA for 7 hours and 25 minutes, and then charged at a constant voltage of 2.65V for 7 hours and 25 minutes. Thus, the second single reversal of the positive and negative polarities of the battery in this embodiment and the subsequent charging or charge-discharge operation are completed. At this time, the electrode state of the battery has been changed from A- / B+ to A+ / B-. Then, electrode A is made to work as the positive electrode and electrode B is made to work as the negative electrode, so that the battery re-enters the same discharge-charge cycle working system as before to carry out the 32nd working discharge and subsequent cycles. The results show that after the second single positive and negative polarity reversal and subsequent charging or charge-discharging operations, the discharge capacity of the battery in the 32nd cycle working state is 1189mAh, which should be related to the full charging of the battery after the polarity reversal. The total charging capacity of the battery between this polarity reversal and the resumption of battery cycle operation is 6659mAh.Next, allow the battery to continue to operate under the working system, such as. Figure 2 As shown, during the 32nd to 45th cycle operation, the electrode state of the battery of this embodiment is A+ / B-, at this time, a positive electrode reaction occurs on electrode A, and a negative electrode reaction occurs on electrode B. The discharge capacity of the battery of this embodiment during the 32nd to 45th cycle operation drops from 1189 mAh to 787 mAh.

[0084] During the cyclic charge and discharge operation of the lead-acid battery of this embodiment, the single positive and negative polarity reversal and the subsequent charging or charge and discharge operation similar to the first or second time described above in this embodiment are repeatedly, multiple times and interspersed, that is, the third, fourth, ..., ninth single positive and negative polarity reversal and the subsequent charging or charge and discharge operation performed or performed between the 45th and 46th times, the 55th and 56th times, the 64th and 65th times, the 73rd and 74th times, the 82nd and 83rd times, the 94th and 95th times, the 104th and 105th times of the lead-acid battery of this embodiment during its cyclic operation are realized. Figure 2 The middle mark shows the polarity state or polarity direction of the electrodes A and B of the lead-acid battery of this embodiment before or after the single positive and negative polarity reversal and the subsequent charging or charging and discharging operation of this embodiment during the cyclic charging and discharging operation. In the 46th and subsequent cyclic working system of the lead-acid battery of this embodiment, the charging method is changed to charging it with a constant current of 222mA after the working discharge is completed, and when the battery voltage reaches 2.65V, it is switched to a constant voltage of 2.65V to continue charging the battery. The total time of two (constant current, constant voltage) charging is 8 hours and 24 minutes.

[0085] like Figure 2 As shown, the working discharge capacity of the lead-acid battery of this embodiment is improved or restored year-on-year. On the one hand, as described above, this embodiment is improved, repaired, reversed, eliminated, suppressed, and prevented, so that the working discharge capacity of the lead-acid battery of this embodiment in the cycle operation is improved or restored after the operation. During the normal cycle operation of the lead-acid battery of this embodiment, the positive and negative polarity reversal of this embodiment and the subsequent charge and discharge or charge and discharge operation of this embodiment are performed regularly or irregularly (for example, in a manner of specifying the number of cycle operations) and interspersedly, which will effectively improve, repair, reverse, eliminate, suppress, and prevent the softening and / or shedding problem of the positive active material, thereby improving or extending the service life of the lead-acid battery of this embodiment.

[0086] In this embodiment, rapid charge and discharge pulse current and pulse voltage may also be used to perform the positive and negative polarity reversal and subsequent charging or charge and discharge operations of this example.

[0087] Some experimental data in this embodiment show that the degree of recovery of the working discharge capacity of the lead-acid battery of this embodiment after each single polarity reversal and subsequent charging or charge-discharging operation, and the number of charge-discharge cycles of the lead-acid battery of this embodiment that can continuously maintain a normal or higher discharge capacity after each working discharge capacity recovery (i.e., the number of charge-discharge cycles of the lead-acid battery of this embodiment with a normal or higher working discharge capacity between each single polarity reversal and subsequent charging or charge-discharging operation) are different depending on the current, voltage, time, charge-discharge capacity, pulse or direct current, internal resistance of the battery, electrolyte density, and electrolyte saturation, and the method used in each single polarity reversal and subsequent charging or charge-discharging operation.

[0088] According to the specific capacity of 61mAh / g (2h rate, 25°C) of the positive electrode active material of the current commercial power lead-acid battery under rated working conditions, the rated capacity of the lead-acid battery electrode of this embodiment is 821mAh (based on the average mass of the active material of a single electrode of the lead-acid battery of this embodiment mentioned above). If the discharge capacity is lower than the rated capacity or 80% of the rated capacity (657mAh) for three consecutive times at the 100% discharge depth as the basis for judging the end of the battery life, then Figure 2 As shown, according to the discharge capacity attenuation trend line of the 1st to 15th times, it can be considered that the service life of the lead-acid battery of this embodiment will be basically 25 times and 36 times respectively without the reversal of the positive and negative polarities of this embodiment and the subsequent charging or charge-discharge operation. However, in fact, after the reversal of the positive and negative polarities of this embodiment and the subsequent charging or charge-discharge operation, the working discharge capacity of the battery remains above the rated capacity after the 111th cycle operation, and the service life of the battery is significantly improved or extended. It can be inferred that, excluding factors such as short circuit, open circuit, water loss, and pollution that cause battery failure, the method of improving or extending the service life of the lead-acid battery of this embodiment will make the service life of the lead-acid battery of this example be further improved or extended on the basis of 111 cycles. The active material utilization rate of the lead-acid battery electrode of this embodiment when working as a positive electrode is significantly higher than the active material utilization rate of the positive electrode of the current commercial power lead-acid battery, which is mainly related to the thickness of the electrode of this embodiment and the collector structure.

[0089] The two electrodes of the lead-acid storage battery in this embodiment are also equivalent positive and negative universal electrodes to each other, because after the electrodes are formed, the two have the same functions and performances. However, in actual use, changes and differences in factors such as polarity reversal and subsequent charging or charging and discharging operation systems, and cyclic working systems will lead to differences in the functions and performances of the two.

[0090] Example 4

[0091] The lead-acid battery pack in this embodiment is a full-tube lead-acid battery pack with a rated voltage of 4V and a rated capacity of 539mAh (C 3.5 , 3.5h rate, 25℃) is composed of two identical full-tube lead-acid batteries connected in series, all electrodes of each full-tube lead-acid battery are tubular electrodes, and these tubular electrodes are positive and negative common electrodes (i.e., electrodes common to the positive and negative electrodes), and these tubular positive and negative common electrodes are the same in electrode structure and active material formula, the inner diameter of the casing of each tubular positive and negative common electrode is 6.3mm, the height of the casing is 75mm (including the tube plug), the diameter of the lead-calcium alloy conductive bone core in the casing is 2.5mm, and each full-tube lead-acid battery includes 3 tubular positive and negative electrodes For the convenience of the subsequent description of this embodiment, the six tubular positive and negative common electrodes of the lead-acid battery group of this embodiment are named as electrodes A1, A2, A3, A4, B1, and B2, respectively. The arrangement of these six electrodes in each full-tubular lead-acid battery in the lead-acid battery group of this embodiment is as follows: electrode B1 is sandwiched between electrodes A1 and A2 or electrode B2 is sandwiched between electrodes A3 and A4. The mass of the active material in the sleeve of electrode A1 or A2 or A3 or A4 is 5.8 g, the mass of the active material in the sleeve of electrode B1 or B2 is 5.5 g, and the mass of the active material in the sleeve of electrode A1, A2, A3 is 5.8 g. The active materials in A1, A2, A3, and A4 are all composed of ball-milled lead powder and barium sulfate (0.8 wt % relative to the ball-milled lead powder). The two output terminals of the lead-acid battery pack of this embodiment are named battery pack terminals A and B, respectively, wherein the battery pack terminal A is connected to the electrode A1 or A2 or A3 or A4, and the battery pack terminal B is connected to the electrode B1 or B2. During the initial cycle charge and discharge operation of the lead-acid battery pack of this embodiment, the electrodes A1, A2, A3, and A4 are used as positive electrodes for cycle operation (i.e., during the cycle operation, the electrodes A1, A2, A3, and A4 are subjected to lead sulfate). The positive and negative tubular electrodes are separated by a separator. The density of the electrolyte sulfuric acid solution used in the lead-acid battery in this embodiment is 1.27 g / cm 3 This embodiment eliminates or prevents factors such as fluid loss, open circuit, short circuit, mechanical damage, and test failure from interfering with the implementation process and results of this embodiment.

[0092] The method for improving or extending the service life of the lead-acid battery pack of the present embodiment is that, whenever the lead-acid battery pack of the present embodiment has been cycled for a certain number of times or the working discharge and charge capacity has dropped to a certain extent due to softening or / and shedding of the positive electrode active material, the positive and negative electrodes of the lead-acid battery pack of the present embodiment are automatically or / and manually subjected to a single polarity reversal and subsequent charging or charging and discharging operation, so as to improve, repair, reverse, prevent, inhibit, and eliminate the problem of reduced working discharge capacity or working capacity and end of service life caused by softening and shedding of the positive electrode active material, so that the working discharge capacity or working capacity of the lead-acid battery pack of the present embodiment is restored or improved, and then after the polarity reversal and subsequent charging or charging and discharging operation, the lead-acid battery pack of the present embodiment is put back into the cycle charging and discharging operation with the electrode polarity state after the polarity reversal to perform cycle work until the next positive and negative polarity reversal and subsequent charging or charging and discharging operation is started. After the polarity reversal and the subsequent charging or charging and discharging operation, the lead-acid battery pack of this embodiment is put back into the cyclic charging and discharging operation to perform cyclic operation with the electrode polarity state after the polarity reversal. For example, if the electrodes A1, A2, A3, and A4 of the lead-acid battery pack of this embodiment are used as positive electrodes for cyclic operation before the polarity reversal (i.e., the charging and discharging process of the positive electrode reaction of the lead-acid battery occurs on the electrodes A1, A2, A3, and A4 during the cyclic operation), then after the polarity reversal, the electrodes A1, A2, A3, and A4 are used as negative electrodes for cyclic charging and discharging (i.e., the charging and discharging process of the negative electrode reaction of the lead-acid battery occurs on the electrodes A1, A2, A3, and A4 during the cyclic operation). If the corresponding electrodes B1 and B2 are used as negative electrodes for circulation work before the polarity reversal (i.e., the charging and discharging process of the negative electrode reaction of the lead-acid battery occurs on the electrodes B1 and B2 during the circulation work), then they are used as positive electrodes for circulation work after the polarity reversal (i.e., the charging and discharging process of the positive electrode reaction of the lead-acid battery occurs on the electrodes B1 and B2 during the circulation work). Similarly, if the polarity state or polarity direction of the electrodes A1, A2, A3, A4 or the electrodes B1 and B2 in the circulation work process before the polarity reversal is opposite, then the polarity state or polarity direction of the electrodes A1, A2, A3, A4 or the electrodes B1 and B2 in the circulation work process after the polarity reversal is also opposite. The triggering method for triggering or starting any polarity reversal of the positive and negative electrodes of the lead-acid battery pack of this embodiment and the subsequent charging or charge-discharging operation can be manually triggered or automatically triggered by the program according to the reaching of a preset trigger condition. The triggering condition can be one or more of a certain number of cyclic charge and discharge operations or the cumulative number of times, charge amount, discharge amount, charge and discharge rate, current change, voltage change, etc., or their calculated values.

[0093] The cyclic charge and discharge working system adopted by the lead-acid battery pack in this implementation is: when working and discharging, the charge and discharge cycle is 0.283C.3.5 The current is discharged to 3.5V, and then, at 0.338C 3.5 The battery is then charged at a constant current of 5.95 V or for 9 hours and 24 minutes, and then charged at a constant voltage of 5.3 V for 3 hours, and then the previous discharge process is repeated, and this process is repeated and cycled to make the lead-acid battery pack of this embodiment work in a cyclic charge and discharge operation.

[0094] The implementation results of the lead-acid battery pack cycle operation and the method of improving or extending the service life of the lead-acid battery pack of this embodiment are as follows: Figure 3 As shown, during the cyclic operation of the lead-acid battery pack of this embodiment, between the 6th and 7th, between the 17th and 18th, between the 25th and 26th, between the 33rd and 34th, between the 41st and 42nd, between the 56th and 57th working cycles, a single positive and negative polarity reversal and subsequent charging or charging and discharging operation is performed or performed for the first, second, ..., and sixth time in sequence. The method or process of the positive and negative polarity reversal and subsequent charging or charging and discharging operation is as follows:

[0095] For the first single positive and negative polarity reversal and the subsequent charging or charging and discharging operation: when the lead-acid battery pack of this embodiment is in the charging state after completing the sixth cycle, at this time, the polarities of electrodes A1, A2, A3, and A4 are positive, and the polarities of electrodes B1 and B2 are negative, the cycle of the lead-acid battery pack of this embodiment is stopped, and the positive and negative output terminals of the charging and discharging device are reversely connected to the positive and negative output terminals of the lead-acid battery pack of this embodiment, that is, the positive output terminal of the charging and discharging device is connected to the negative output terminal of the lead-acid battery pack of this embodiment (battery terminal B1). ), the negative output terminal of the charging and discharging device is connected to the positive output terminal of the lead-acid battery pack of this embodiment (battery pack terminal A), and after the reverse polarity is connected, the charging and discharging device measures the voltage of the lead-acid battery pack of this embodiment to be -5.53V. Then, the lead-acid battery pack of this embodiment is charged with a current of 458mA in the reverse polarity connection state, so that the voltage of the positive and negative output terminals of the lead-acid battery pack of this embodiment (the value measured by the charging and discharging device, the same below in this embodiment) rises from -5.53V to 0V and then to 5.8V. In this process, the lead-acid battery pack of this embodiment The battery pack undergoes the first polarity reversal, that is, in the process of rising from -5.53V to 0V, the discharge process of the positive electrode reaction of the lead-acid battery mainly occurs on electrodes A1, A2, A3, and A4, and the discharge process of the negative electrode reaction of the lead-acid battery mainly occurs on electrodes B1 and B2. In the process of rising from 0V to 5.8V, the charging process of the negative electrode reaction of the lead-acid battery mainly occurs on electrodes A1, A2, A3, and A4, and the charging process of the positive electrode reaction of the lead-acid battery mainly occurs on electrodes B1 and B2. With the connection state between the standby output end and the output terminal of the lead-acid battery pack of this embodiment unchanged, the lead-acid battery pack of this embodiment is discharged at 152.7 mA for 14 minutes to 3.5 V, and then charged at a constant current of 229 mA for 8 hours to 5.72 V, and then discharged at 152.7 mA for 2 minutes to 4.5 V, and then charged at a constant current of 114 mA for 3 hours to 5.5 V, and then the lead-acid battery pack of this embodiment is put into the 7th working discharge process of the cycle work, and the 7th and subsequent cycles are carried out until the 17th cycle. In the 7th to 17th cycles of the lead-acid battery pack of this embodiment, the polarity of the battery pack terminal A is negative, and the polarity of the electrode pool terminal B is positive, such as Figure 3 As shown, that is, during this process, the charge and discharge process of the negative electrode reaction of the lead-acid battery occurs on the electrodes A1, A2, A3, and A4, and the charge and discharge process of the positive electrode reaction of the lead-acid battery occurs on the electrodes B1 and B2.

[0096] For the second single positive and negative polarity reversal and the subsequent charging or charging and discharging operation: when the lead-acid battery pack of this embodiment is in the charging state after completing the 17th cycle, at this time, the polarities of electrodes A1, A2, A3, and A4 are negative, and the polarities of electrodes B1 and B2 are positive, the cycle of the lead-acid battery pack of this embodiment is stopped, and the positive and negative output terminals of the charging and discharging device are reversely connected to the positive and negative output terminals of the lead-acid battery pack of this embodiment at this time, that is, the positive output terminal of the charging and discharging device is connected to the negative output terminal of the lead-acid battery pack of this embodiment at this time (battery terminal A). The negative output terminal of the charging and discharging device is connected to the positive output terminal (battery terminal B) of the lead-acid storage battery pack of this embodiment at this time. After the reverse polarity connection, the charging and discharging device measures the voltage of the lead-acid storage battery pack of this embodiment to be -4.54V. Then, the lead-acid storage battery pack of this embodiment is charged with a current of 459mA in the reverse polarity connection state, so that the output voltage (the value measured by the charging and discharging device, the same below in this embodiment) of the lead-acid storage battery pack of this embodiment rises from -4.54V to 0V and then to 5.8V, which takes 4 hours and 30 minutes. During this process, the lead-acid storage battery pack of this embodiment The battery pack undergoes a second polarity reversal, that is, in the process of rising from -4.54V to 0V, the discharge process of the negative electrode reaction of the lead-acid battery mainly occurs on electrodes A1, A2, A3, and A4, and the discharge process of the positive electrode reaction of the lead-acid battery mainly occurs on electrodes B1 and B2. In the process of rising from 0V to 5.8V, the charging process of the positive electrode reaction of the lead-acid battery mainly occurs on electrodes A1, A2, A3, and A4, and the charging process of the negative electrode reaction of the lead-acid battery mainly occurs on electrodes B1 and B2. With the connection state between the output terminal and the output terminal of the lead-acid battery pack of this embodiment unchanged, the lead-acid battery pack of this embodiment is discharged at 152.7 mA for 17 minutes to 3.5 V, and then charged at a constant current of 229 mA for 8 hours to 5.41 V, and then discharged at 152.7 mA for 2 minutes to 4.23 V, and then charged at a constant current of 114 mA for 3 hours to 5.26 V, and then the lead-acid battery pack of this embodiment is put into the 18th working discharge process in the cycle work, and the 18th and subsequent cycles to the 25th cycle work are performed. In the 18th to 25th cycle work of the lead-acid battery pack of this embodiment, the polarity of the battery pack terminal A is positive, and the polarity of the electrode pool terminal B is negative, such as Figure 3 As shown, that is, during this process, the charging and discharging process of the positive electrode reaction of the lead-acid battery occurs at the electrodes A1, A2, A3, and A4, and the charging and discharging process of the negative electrode reaction of the lead-acid battery occurs at the electrodes B1 and B2, that is, the polarity state or polarity direction of the battery terminals A and B and the electrodes A1, A2, A3, A4, B1, and B2 returns to the state when the lead-acid battery pack of this embodiment is initially cycled.

[0097] During the cyclic operation of the lead-acid battery pack of the present embodiment, the single positive and negative polarity reversal and the subsequent charging or charge-discharging operation similar to the first or second time in the present embodiment as described above are repeatedly, multiple times, and interspersed, that is, the third, fourth, fifth, sixth, ..., and Yth single positive and negative polarity reversal and the subsequent charging or charge-discharging operation (X and Y are positive integers) of the lead-acid battery pack of the present embodiment are performed or performed between the 25th and 26th times, the 33rd and 34th times, the 41st and 42nd times, the 56th and 57th times, ..., the Xth and X+1th times of its working cycle. Figure 3 The middle mark shows the polarity state or polarity direction of the battery terminal A and B during the cycle operation of the lead-acid battery pack of this embodiment before or after each single positive and negative polarity reversal and subsequent charging or charging and discharging operation. Figure 4 23-28 cycle charge and discharge operation process of the lead-acid battery pack of this embodiment and the current and voltage changes during the third single positive and negative polarity reversal and the subsequent charging or charging and discharging operation process interspersed during the process are shown in the figure. The third single positive and negative polarity reversal and the subsequent charging or charging and discharging operation process are basically the same as the first single positive and negative polarity reversal and the subsequent charging or charging and discharging operation process. The difference is that after the step of "discharging at 152.7mA for 2 minutes and then charging at a constant current of 114mA for 3 hours" in the later stage of the operation is completed, it is discharged at a current of 153mA for 2 hours and 58 minutes, and then the lead-acid battery pack of this embodiment is put into the 26th cycle operation.

[0098] like Figure 3As shown, after completing each single polarity reversal and the subsequent charging or charging and discharging operation, the working discharge capacity of the lead-acid battery pack of this embodiment is improved or restored year-on-year. After inspection, this is because the positive and negative polarity reversal and the subsequent charging and discharging or charging and discharging operation of this embodiment improve, repair, reverse, inhibit, eliminate, and prevent the softening or / and shedding of the positive active material of the lead-acid battery pack of this embodiment. During the normal cycle operation of the lead-acid battery pack of this embodiment, the positive and negative polarity reversal and the subsequent charging and discharging or charging and discharging operation of this embodiment are performed regularly or irregularly (for example, in a manner of specifying the number of cycle operations) and interspersed on the lead-acid battery pack of this embodiment, which will effectively improve, repair, reverse, eliminate, inhibit, and prevent the softening or / and shedding of the positive active material, thereby improving or extending the life of this embodiment. The service life of the lead-acid battery pack of the embodiment, for example, because the electrodes A1, A2, A3, A4, B1, and B2 are repeatedly and alternately used as positive electrodes or negative electrodes for charge and discharge cycles, the electrode corrosion problem generated when working as the positive electrode is improved, repaired, and reversed when the electrode is used as the negative electrode for charge and discharge cycles, thereby also delaying, improving, repairing, reversing, and preventing the corrosion problem of the lead-acid battery pack of this embodiment during long-term use, which is also conducive to greatly improving or extending the service life of the lead-acid battery pack of this embodiment. It can be inferred that, under the condition of excluding factors such as short circuit, open circuit, water loss, pollution, etc. that cause battery failure, the method for improving or extending the service life of the lead-acid battery pack of this embodiment will enable the service life of the lead-acid battery pack of this embodiment to be further improved or extended on the basis of the existing effective cycle number.

[0099] In this embodiment, rapid charge and discharge pulse current and pulse voltage may also be used to perform the positive and negative polarity reversal and subsequent charging or charge and discharge operations of this example.

[0100] The degree of recovery of the working discharge capacity of the lead-acid battery pack of this embodiment after the operation and the number of charge-discharge cycles of normal or higher discharge capacity that can be continuously maintained after each working discharge capacity recovery of the lead-acid battery pack of this embodiment (i.e., the number of charge-discharge cycles of normal operation or higher discharge capacity of the lead-acid battery pack of this embodiment after each single polarity reversal and the subsequent charging or charge-discharge operation) vary with the current, voltage, time, charge-discharge capacity, pulse or direct current, internal resistance of the battery or battery pack, electrolyte density, and electrolyte saturation used in each single polarity reversal and the subsequent charging or charge-discharge operation.

[0101] In other implementations of the present embodiment, the positive and negative electrodes or all electrodes of the full tubular lead-acid battery pack of the present embodiment are the same kind of tubular positive and negative universal electrodes, that is, without considering the manufacturing errors generated when manufacturing the electrodes, all electrodes or all tubular electrodes of the full tubular lead-acid battery pack of the present embodiment are completely identical to each other in all electrode structures and manufacturing aspects (such as electrode structure, shape, conductive bone core, sleeve, collector, active material formula and quality, manufacturing process, etc.) before being formed. After being formed, each tubular electrode of the full tubular lead-acid battery pack of the present embodiment is formed into a positive electrode or a negative electrode respectively.

[0102] In other implementations of this embodiment, the positive and negative electrodes or all electrodes of the all-tubular lead-acid battery pack of this embodiment are tubular positive and negative universal electrodes that are equivalent to each other, that is, after the electrodes are formed or charged and discharged, during the operation or use of the lead-acid battery pack, without considering error factors, the tubular electrodes of this embodiment have or exhibit the same functions and performances.

[0103] Example 5

[0104] The lead-acid battery pack of the present embodiment includes a flat grid lead-acid battery, a tubular lead-acid battery, a wound lead-acid battery, a bipolar lead-acid battery, a horizontal lead-clad lead-acid battery, a foam grid lead-acid battery, a valve-regulated sealed lead-acid battery, a colloidal lead-acid battery, a lead-carbon battery, a supercapacitor-lead-acid battery, or one or more thereof. The rated voltage U of the lead-acid battery pack of the present embodiment is 6V, 12V, 24V, 36V, 48V, 60V, or 72V. The rated capacity (C2,2 small) of the lead-acid battery pack of the present embodiment is The lead-acid battery pack of this embodiment has a battery pack output terminal A and a battery pack output terminal B. The battery pack output terminal A is conductively connected to the electrodes A1, A2, ..., An (n = a positive integer) in the lead-acid battery pack of this embodiment, and the battery pack output terminal B is conductively connected to the electrodes B1, B2, ..., Bn (n = a positive integer) in the lead-acid battery pack of this embodiment. The electrodes A1, A2, ..., An, B1, B2, ..., Bn in the lead-acid battery pack of this embodiment are all common positive and negative electrodes (i.e., electrodes common to the positive and negative electrodes), which can be used or work as the positive electrode of the lead-acid battery, and can also be used or work as the negative electrode of the lead-acid battery. In the initial cycle charge and discharge operation process of the lead-acid battery pack of this embodiment, the polarity of the battery pack output terminal A is positive and the polarity of the battery pack output terminal B is negative, that is, in the initial cycle operation process of the lead-acid battery pack of this embodiment, the charge and discharge process of the positive electrode reaction of the lead-acid battery occurs on the electrodes A1, A2, ..., An, and the charge and discharge process of the negative electrode reaction of the lead-acid battery occurs on the electrodes B1, B2, ..., Bn. A separator is provided between the positive and negative electrodes.

[0105] The method for improving or extending the service life of the lead-acid battery pack of the present embodiment is that when the lead-acid battery pack of the present embodiment reaches a certain number of working cycles during its cyclic use or operation, or when it is needed (for example, when the working discharge capacity of the lead-acid battery pack of the present embodiment decreases and is lower than a certain capacity value due to the softening of the positive electrode active material, it is desired or necessary to increase the working discharge capacity of the battery pack or to improve or extend the service life of the battery pack), between two working cycles, the lead-acid battery pack of the present embodiment is automatically or / and manually reversed once for the positive and negative poles and then charged or charged and discharged, so as to improve, eliminate, reverse, inhibit, and prevent the softening problem of the positive electrode active material, so that the lead-acid battery pack of the present embodiment can be improved, eliminated, reversed, inhibited, and prevented from softening. The working capacity of the lead-acid battery pack of this embodiment is restored or improved. After the positive and negative polarity reversal and the subsequent charging or charging and discharging operation are completed, the lead-acid battery pack of this embodiment is put into the charging and discharging cycle work or work in the polarity state after the polarity reversal, until the positive and negative polarity reversal and the subsequent charging or charging and discharging operation of the lead-acid battery pack of this embodiment are triggered or started again. In this way, the cyclic work of the lead-acid battery pack of this embodiment and the positive and negative polarity reversal and the subsequent charging or charging and discharging operation of the lead-acid battery pack of this embodiment are intermittently, interspersed, and alternately performed or occurred, thereby improving or extending the service life of the lead-acid battery pack of this embodiment.

[0106] The first single positive and negative polarity reversal and subsequent charging or charging and discharging operation of the lead-acid battery pack of this embodiment includes the following steps: when the lead-acid battery pack of this embodiment is in the initial cycle operation process (during this period, the polarity of the output terminal A of the lead-acid battery pack of this embodiment is positive, and the polarity of the output terminal B is negative, that is, the charging and discharging process of the positive electrode reaction of the lead-acid battery occurs on the electrodes A1, A2, ..., An, and the charging and discharging process of the negative electrode reaction of the lead-acid battery occurs on the electrodes B1, B2, ..., Bn) Process), when the working cycle reaches a certain number of times, for example, 5 times, 9 times, 20 times or 60 times, the lead-acid battery pack of this embodiment is reversely charged, and the reverse charging method includes one or more of single stage, multi-stage, constant current (for example, 0.1C2, 0.5C2, 1.2C2, 6C2), constant voltage (for example, U, 1.3U, 2U, 5U), positive pulse, negative pulse, and finally the polarity of the output terminals A and B of the lead-acid battery pack of this embodiment is changed, so that the electrodes A1, A2, .... .., An, B1, B2, ... Bn, the polarity is reversed, and, after the polarity reversal, the lead-acid storage battery group of this embodiment is charged or discharged, and the charging or charging and discharging method includes one or more of a single stage, a multi-stage, a constant current (for example, 0.15C2, 0.4C2, 0.8C2, 7C2), a constant voltage (for example, 0.8U, 1.5U, 2U, 4U), a positive pulse, and a negative pulse. Then, the lead-acid storage battery group of this embodiment is recharged in the polarity state after the polarity reversal. The lead-acid battery pack of this embodiment is put into circulation work to carry out circulation work. During the circulation work process after completing the first single positive and negative polarity reversal and the subsequent charging or charge-discharge operation, the polarity of the output terminal A of the lead-acid battery pack of this embodiment is negative and the polarity of the output terminal B is positive, that is, the charge and discharge process of the negative electrode reaction of the lead-acid battery occurs on the electrodes A1, A2, ..., An, and the charge and discharge process of the positive electrode reaction of the lead-acid battery occurs on the electrodes B1, B2, ..., Bn.

[0107] The second single positive and negative polarity reversal and subsequent charging or charging and discharging operation of the lead-acid storage battery of this embodiment comprises the following steps: when the lead-acid storage battery of this embodiment is in a cyclic operation process after the first single positive and negative polarity reversal and subsequent charging or charging and discharging operation (during this period, the polarity of the output terminal A of the lead-acid storage battery of this embodiment is negative, and the polarity of the output terminal B is positive, that is, the charging and discharging process of the negative electrode reaction of the lead-acid storage battery occurs on the electrodes A1, A2, ..., An, and the electrodes B1, B2, ..., Bn When the working cycle completes a certain number of times, for example, 9 times, 13 times, 20 times or 40 times, the lead-acid battery pack of this embodiment is subjected to a second reverse polarity charging, wherein the reverse polarity charging method includes one or more of a single stage, a multi-stage, a constant current (for example, 0.2C2, 0.5C2, 1.5C2, 3C2), a constant voltage (for example, U, 1.1U, 2U, 4U), a positive pulse, and a negative pulse, and finally the output terminals A and B of the lead-acid battery pack of this embodiment are polarized. The polarity of the electrodes A1, A2, ..., An, B1, B2, ..., Bn is reversed, and after the polarity reversal, the lead-acid storage battery of this embodiment is charged or discharged, and the charging or charging and discharging method includes one or more of a single stage, a multi-stage, a constant current (for example, 0.18C2, 0.7C2, 2C2, 5C2), a constant voltage (for example, 0.6U, 1.3U, 2.2U, 3U), a positive pulse, and a negative pulse. Then, the lead-acid storage battery of this embodiment is charged or discharged after the polarity reversal. polarity state, and re-enter the cycle work to carry out the cycle work. In the cycle work process carried out after the lead-acid battery pack of this embodiment completes the second single positive and negative polarity reversal and the subsequent charging or charge-discharge operation, the polarity of the output terminal A of the lead-acid battery pack of this embodiment is positive, and the polarity of the output terminal B is negative, that is, the charge and discharge process of the positive electrode reaction of the lead-acid battery occurs on the electrodes A1, A2, ..., An, and the charge and discharge process of the negative electrode reaction of the lead-acid battery occurs on the electrodes B1, B2, ..., Bn.

[0108] During the cyclic charge-discharge operation of the lead-acid battery pack of this embodiment, the method of implementing other single positive and negative polarity reversals and subsequent charging or charging and discharging operations is similar to the method of implementing the first or second single positive and negative polarity reversals and subsequent charging or charging and discharging of the above-mentioned embodiment. In this way, during the cyclic charge-discharge operation of the lead-acid battery pack of this embodiment, the positive and negative polarity reversals and subsequent charging or charging and discharging operations of the above-mentioned embodiment are repeatedly, multiple times, and interspersed, so that the softening and / or shedding of the positive active material of the lead-acid battery pack of this embodiment is improved, repaired, reversed, eliminated, suppressed, and prevented, thereby improving or extending the working discharge capacity and service life of the lead-acid battery pack of this embodiment.

[0109] In other implementations of the present embodiment, the method for improving or extending the service life of the lead-acid battery group of the present embodiment is as follows: during the cyclic operation of the lead-acid battery group of the present embodiment, in order to improve, repair, reverse, solve, and prevent the battery group's working capacity from decreasing or its service life from being terminated due to the softening and / or shedding of the positive active material, the lead-acid battery group of the present embodiment is subjected to odd or even numbers of positive and negative polarity reversals and subsequent charging or charge-discharging operations in multiple periods and interspersed manner; after completing the odd or even numbers of positive and negative polarity reversals and subsequent charging or charge-discharging operations in each period, the lead-acid battery group of the present embodiment is put back into the charge-discharge cycle operation or operation in the polarity state after the polarity reversal in that period, so that the working capacity of the lead-acid battery group of the present embodiment is restored or improved, until another period of odd or even numbers of positive and negative polarity reversals and subsequent charging or charge-discharging operations on the lead-acid battery group of the present embodiment is triggered or started again. Any of the odd or even number of positive and negative polarity reversals and the subsequent charging or charging and discharging operations in each period is similar to the first or second single positive and negative polarity reversal and the subsequent charging or charging and discharging operation described above in this embodiment.

[0110] In other implementations of this embodiment, the positive electrode, the negative electrode or all electrodes of the lead-acid battery pack of this embodiment are the same kind of common positive and negative electrodes, that is, without considering the manufacturing errors generated when manufacturing the electrodes, all electrodes of the lead-acid battery pack of this embodiment are completely identical to each other in all electrode compositions and manufacturing aspects (such as electrode structure, shape, current collector, current sink, active material formula and quality, other accessories, manufacturing process, etc.) before being formed. After being formed, each electrode of the lead-acid battery pack of this embodiment is formed into a positive electrode or a negative electrode, respectively.

[0111] In other implementations of this embodiment, the positive and negative electrodes or all electrodes of the lead-acid battery pack of this embodiment are universal positive and negative electrodes that are equivalent to each other, that is, after the electrodes are formed or charged and discharged, during the operation or use of the lead-acid battery pack, without considering error factors, the electrodes of this embodiment have or exhibit the same functions and performances.

[0112] Example 6

[0113] This embodiment is the same as or includes: Embodiment 1 to Embodiment 21 described in Chinese Patent Application No. 201710975570.6, that is, all embodiments described in Patent Application No. 201710975570.6.

Claims

1. A method for solving the softening and falling off problem of positive electrode active material in lead-acid batteries or battery packs, characterized in that: The solution is to reverse, repair, improve and eliminate the softening and shedding problems of the positive electrode active material; The lead-acid battery has the problem of softening and falling off of the positive electrode active material; The method comprises: reversing the polarity of the positive electrode and the negative electrode of the lead-acid battery or / and the lead-acid battery group and then performing charging or charging and discharging operations, so that the softening and shedding problems of the positive electrode active material of the lead-acid battery that have occurred are reversed, repaired, improved, or eliminated; Alternatively, the method is: converting the positive electrode or the positive electrode active material of the lead-acid battery into lead, and then converting the lead into PbO2, so that the softening and shedding problems of the positive electrode active material of the lead-acid battery that have occurred are reversed, repaired, improved, and eliminated; Alternatively, the method is: converting the positive electrode or the positive electrode active material of the lead-acid battery into lead or performing a negative electrode electrochemical reaction, converting the negative electrode or the negative electrode active material into PbO2 or performing a positive electrode electrochemical reaction, so that the softening and shedding problems of the positive electrode active material that have occurred in the lead-acid battery can be reversed, repaired, improved, and eliminated.

2. The method for solving the softening and falling off problem of positive electrode active material in lead-acid batteries or battery packs according to claim 1 is characterized in that: The lead-acid battery positive electrode does not contain barium sulfate; The lead-acid battery has a problem of softening or shedding of the positive electrode active material, and the battery capacity decays or the battery life ends due to or mainly due to the softening or shedding of the positive electrode active material; The method comprises: performing polarity reversal and subsequent charging or charge-discharging operation on the positive and negative electrodes of the lead-acid storage battery or / and the lead-acid storage battery group, wherein the operation is performed or is performed twice or an even number of times; and after the cumulative number of times of performing the operation is twice or an even number of times, the softening and shedding problems of the positive electrode active material that have occurred in the lead-acid storage battery are reversed, repaired, improved, and eliminated, and the battery capacity of the lead-acid storage battery whose capacity attenuation decreases and whose life span has been terminated is improved and increased by reversing, repairing, improving, and eliminating the softening and shedding problems of the positive electrode active material.

3. The method for solving the softening and falling off problem of positive electrode active material in lead-acid batteries or battery packs according to claim 2, characterized in that: Before the positive and negative polarity reversal and the subsequent charging or charge-discharging operation, the lead-acid battery is: the capacity drops to below its rated capacity, or the battery capacity shows a decrease when compared to the capacity value of any discharge in the 2nd to 148th or 18th to 50th charge-discharge cycle after the battery is formed.

4. The method for solving the softening and falling off problem of positive electrode active material in lead-acid batteries or battery packs according to claim 3 is characterized in that: Before the positive and negative polarity reversal and the subsequent charging or charging and discharging operation, the lead-acid battery has a capacity that drops to less than 93%, 85.5%, 83%, 80% of its rated capacity or has dropped to 7.3%, 24.9%, 50.3%, 60%, 75%, 80%, 90% or 95% of the rated capacity.

5. The method for solving the softening and falling off problem of positive electrode active material in lead-acid batteries or battery packs according to claim 1, characterized in that: The positive electrode and the negative electrode of the lead-acid battery both contain barium sulfate; The lead-acid battery has a problem of softening or shedding of the positive electrode active material, and the battery capacity decays or the battery life ends due to or mainly due to the softening or shedding of the positive electrode active material; The method comprises: performing polarity reversal and subsequent charging or charge-discharging operation on the positive and negative electrodes of the lead-acid storage battery or / and the lead-acid storage battery group, wherein the total cumulative number of times the operation is performed or performed is ≥1 time; and after the cumulative number of times the operation is performed is ≥1 time, the softening and shedding problems of the positive electrode active material in the lead-acid storage battery that have occurred are reversed, repaired, improved, and eliminated, and the battery capacity of the lead-acid storage battery that has decreased in capacity attenuation and terminated in service life is improved and increased by reversing, repairing, improving, and eliminating the softening and shedding problems of the positive electrode active material.

6. The method for solving the softening and falling off problem of positive electrode active material in lead-acid batteries or battery packs according to claim 5, characterized in that: When the discharge capacity of the battery drops to a value lower than the discharge capacity during the first or 1-15th cycle after the battery is formed, the positive and negative polarity reversal and subsequent charging or charging and discharging operations are performed; Alternatively, through cyclic charge and discharge and the positive and negative polarity reversal and subsequent charging or charge and discharge operations, the capacity of the lead-acid battery presents or generally presents a gradual decrease in capacity during the cyclic charge and discharge process, increases in capacity during the positive and negative polarity reversal and subsequent charging or charge and discharge operations, then presents or generally presents a gradual decrease in capacity during the cyclic charge and discharge process, and then increases in capacity during the positive and negative polarity reversal and subsequent charging or charge and discharge operations.

7. The method for solving the problem of softening and falling off of positive active material in lead-acid batteries or battery packs according to claim 1, characterized in that The lead-acid battery has a problem of softening or shedding of the positive active material, and the battery capacity decays or the battery life ends due to or mainly due to the softening or shedding of the positive active material; The method comprises: reversing the polarity of the positive and negative electrodes of the lead-acid battery or / and the lead-acid battery group and then performing charging or charging and discharging operations: namely, reducing the voltage between the positive and negative electrodes from 1.75V to 0V, and from 0V to - 1.75V, or / and rising from -1.75V to 0V, from 0V to 1.75V; the softening and falling-off problems of the positive active material in the lead-acid battery that have occurred are reversed, repaired, improved, and eliminated, and the battery capacity of the lead-acid battery whose capacity decay and life end are improved and increased by reversing, repairing, improving, and eliminating the softening and falling-off problems of the positive active material.

8. The method for solving the softening and falling off problem of positive electrode active material in lead-acid batteries or battery packs according to claim 1, characterized in that The lead-acid battery has a problem of softening or shedding of the positive active material, and the battery capacity decays or the battery life ends due to or mainly due to the softening or shedding of the positive active material; The method comprises: reversing the polarity of the positive electrode and the negative electrode of the lead-acid storage battery or / and the lead-acid storage battery group and then performing charging or charging and discharging operations, wherein the operation is performed or performed ≥1 times; and after the operation is performed ≥1 times, the softening and shedding problems of the positive electrode active material of the lead-acid storage battery that have occurred are reversed, repaired, improved, or eliminated, and the battery capacity of the lead-acid storage battery that has decreased in capacity attenuation and ended in service life is improved or increased by reversing, repairing, improving, or eliminating the softening and shedding problems of the positive electrode active material; Alternatively, the method comprises: causing the electrodes of the lead-acid battery or / and the lead-acid battery group to undergo polarity reversal, and after the polarity reversal, causing the electrodes that have undergone the polarity reversal to undergo the following electrochemical reactions: causing the electrode that was the positive electrode before the polarity reversal to undergo a negative electrode reaction of the lead-acid battery after the polarity reversal, causing the lead oxide, basic lead sulfate, and lead sulfate contained in the electrode that was the positive electrode before the polarity reversal to undergo an electrochemical reduction reaction after the polarity reversal, and causing the electrode that was the negative electrode before the polarity reversal to undergo a positive electrode reaction of the lead-acid battery after the polarity reversal, one or more of the following; it is also characterized in that the method is implemented on the lead-acid battery or / and the lead-acid battery group for ≥2 times, and after the operation is performed for ≥2 times, the softening and shedding problems of the positive active material of the lead-acid battery are reversed, repaired, improved, and eliminated, and the battery capacity of the lead-acid battery with reduced capacity decay and terminated life is improved and increased by reversing, repairing, improving, and eliminating the softening and shedding problems of the positive active material.

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