Formation method for prolonging service life of lead-acid storage battery

Abstract

The invention discloses a formation method for prolonging the service life of a lead-acid storage battery, and belongs to the technical field of lead-acid storage battery manufacturing. The method comprises the following steps: (1) acid injection: injecting electrolyte into the lead-acid storage battery, and standing the lead-acid storage battery; (2) preliminary formation: charging; charging is performed; (3) supplementing an electrolyte: injecting the electrolyte into the lead-acid storage battery; (4) final formation: discharging; charging is performed; charging is performed; discharging is conducted; charging is performed; charging is performed; and charging. By accurately controlling the acid injection amount and adjusting the electrolyte amount in stages, the storage battery is in an environment beneficial to generation of alpha-PbO2 in the formation process, and the service life of the storage battery is prolonged. The addition of energy cost for paste mixing and curing and the addition of other additives are not needed, and the content of alpha-PbO2 is increased. And a conventional industrial charging mode is adopted, so that the current density is not high, sufficient formation of the lead paste is ensured, the performance stability and reliability of the lead-acid storage battery are improved, and the lead-acid storage battery has better performance in various application scenes.

Description

Technical Field

[0001] The invention relates to the technical field of lead-acid battery manufacturing, and more particularly to a formation method for improving the service life of a lead-acid battery. Background Art

[0002] Lead-acid batteries are a common energy storage device and are widely used in various fields. However, the traditional lead-acid battery formation method still has room for improvement in terms of improving battery life. For VRLA lead-acid batteries, the main component of the battery's positive electrode active material - lead oxide α-PbO 2 and β-PbO 2 , where α-PbO 2 It is the skeleton of active materials, has a relatively small charge capacity, and plays a role in supporting and extending the life of the battery; β-PbO 2 Depends on α-PbO 2 The charge capacity of the skeleton is higher than that of α-PbO 2 Much stronger, the battery discharge is mainly composed of β-PbO 2 Finish.

[0003] At present, in order to improve the market 2 The content of 4PbO·PbSO is generally produced by high-temperature paste making and high-temperature solidification of the plate, so that more 4PbO·PbSO is generated in the solidified plate lead paste. 4 , so that more α-PbO can be generated during the formation 2 However, this method requires the addition of seed additives, high temperature and paste, high temperature curing and extended battery formation time, and the production cost is too high.

[0004] Therefore, in order to increase the 2 The content of lead-acid batteries, how to use the current low-temperature and paste, low-temperature curing, no additives and other methods, try to control the amount of electrolyte and the formation environment to achieve the improvement of battery performance and life, and develop a formation method to increase the life of lead-acid batteries is an urgent problem that technicians in this field need to solve. Summary of the invention

[0005] In view of this, the present invention provides a formation method for increasing the service life of a lead-acid battery.

[0006] In order to achieve the above object, the present invention adopts the following technical solution:

[0007] A formation method for improving the service life of a lead-acid battery comprises the following steps:

[0008] (1) Acid injection:

[0009] Inject 90%-95% of the designed mass of the electrolyte of the lead-acid battery into the lead-acid battery. The electrolyte has a density of 1.240-1.260g / cm 3 dilute sulfuric acid, and then let the lead-acid battery stand for 1-2 hours. At the end of the standing time, the density of the electrolyte is 1.05±0.025g / cm 3 ;

[0010] (2) Initial formation:

[0011] The first stage: the current density is 2-4mA / cm 2 The current is charged for 1-3h, and the formation temperature is 35-45℃;

[0012] The second stage: the current density is 3-5mA / cm 2 The battery is charged with a current of 20-27 hours, the formation temperature is 40-50℃, and the battery terminal voltage reaches 2.70-2.90V;

[0013] The third stage: the current density is 2-4mA / cm 2 The current is charged for 10-17h, the formation temperature is 35-45℃, and the density of the electrolyte is 1.265-1.290g / cm 3 ;

[0014] (3) Replenishing electrolyte:

[0015] Inject 5%-10% of the designed mass of the electrolyte of the lead-acid battery into the lead-acid battery. The electrolyte has a density of 1.265-1.290g / cm 3 of dilute sulfuric acid;

[0016] (4) Final transformation:

[0017] The fourth stage: the current density is -4~-8mA / cm 2 The current discharge is 2-4h;

[0018] Stage 5: Current density is 3-5 mA / cm 2 The current is charged for 8-12h;

[0019] Stage 6: Current density is 2-4 mA / cm 2 The current is charged for 10-14h;

[0020] The seventh stage: the current density is -3~-6mA / cm 2 The current discharge is 8-12h;

[0021] Stage 8: Current density is 4-8mA / cm 2 The current is charged for 5-8h;

[0022] The ninth stage: with a current density of 3-5 mA / cm 2 The current is charged for 3-5h;

[0023] Stage 10: Current density of 2-4 mA / cm 2 The current is charged for 10-14h.

[0024] The invention mechanism of the present invention is as follows: the present invention injects 90%-95% of the designed mass of the electrolyte of the lead-acid battery into the lead-acid battery, and the electrolyte has a density of 1.240-1.260g / cm 3 Too much electrolyte will make it difficult to form a neutral or alkaline environment inside the battery. Too low a concentration will affect the early formation of the battery. Too high a density will make it difficult to generate α-PbO. 2 , too low density will affect the battery capacity. When standing still, the lead oxide and basic lead sulfate in the lead paste react with H 2 SO 4 Reaction occurs, H 2 SO 4 The concentration of electrolyte decreases. At the end of the static period, the lower limit of the relative density of the electrolyte should not be less than 1.025 g / cm 3 , so as not to affect the battery capacity.

[0025] After standing, the battery is in a relatively alkaline environment, and the basic lead sulfate in the lead paste is oxidized to mainly generate α-PbO 2 , a small amount of β-PbO 2 and some PbSO 4 , at this time α-PbO 2 The relative density of the electrolyte decreases with the increase of β-PbO 2 and PbSO 4 It increases with the increase of the relative density of the electrolyte; at this stage, the initial formation conditions must be strictly controlled to ensure the current density. Too high a current density will increase the temperature rise inside the battery, increase water consumption, and lead to an increase in relative density.

[0026] The first stage: the current density is 2-4mA / cm 2 The current is charged for 1-3h, during this stage, α-PbO is generated. 2 The critical stage of the content of α-PbO is to strictly control the current density, the relative density of the electrolyte within the required range, and the temperature rise must not exceed 45°C, otherwise the formation time of this stage will be shortened, resulting in the formation of α-PbO 2 The content of PbSO is reduced 4 Increased amount and β-PbO 2 Content increased.

[0027] The second stage: the current density is 3-5mA / cm 2The battery is charged with a current of 20-27h, the formation temperature is ≤50℃, the battery terminal voltage reaches 2.70-2.90V, and the water decomposition voltage is reached. The plate will strongly gasify, and the bubbles generated will affect α-PbO 2 phase, so after reaching the voltage requirement, it turns into the third stage.

[0028] The second and third stages are PbSO 4 Conversion to β-PbO 2 At the initial stage of formation, attention should be paid to the control of process parameters, which will make α-PbO 2 The content rises to a plateau, reducing PbSO 4 and β-PbO 2 The content.

[0029] The beneficial effects of the present invention are as follows: 1. By accurately controlling the amount of acid injected and adjusting the amount of electrolyte in stages, the battery is in a state that is conducive to the generation of α-PbO during the formation process. 2 environment, and improve the life of the battery.

[0030] 2. No need to increase the energy cost of paste and curing and add other additives, which greatly improves the α-PbO 2 The content.

[0031] 3. The conventional charging method in the industry is adopted, and the current density is not high, which can ensure that the lead paste is fully formed, improve the performance stability and reliability of the lead-acid battery, and enable it to perform better in various application scenarios. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is an electron microscope observation image of the lead-acid battery of Example 1;

[0033] Figure 2 This is the electron microscope observation picture of the lead-acid battery of Comparative Example 1. DETAILED DESCRIPTION

[0034] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0035] Example 1

[0036] The formation method for improving the service life of a lead-acid battery comprises the following steps:

[0037] (1) Acid injection:

[0038] Inject 90% of the designed mass of the lead-acid battery electrolyte (800g / cell) into the lead-acid battery. The electrolyte has a density of 1.255g / cm 3 dilute sulfuric acid, and then let the lead-acid battery stand for 1.5 hours. At the end of the standing time, the density of the electrolyte is 1.05g / cm 3 ;

[0039] (2) Initial formation:

[0040] The first stage: the current density is 2.35mA / cm 2 The current is charged for 1.5h, and the formation temperature is 42℃. At this time, α-PbO 2 / β-PbO 2 The ratio of PbSO 4 The content is low;

[0041] The second stage: the current density is 4.1mA / cm 2 The battery is charged for 24 hours at a formation temperature of 49°C and the terminal voltage reaches 2.82V. At this time, part of the PbSO 4 Conversion to β-PbO 2 ;

[0042] The third stage: the current density is 2.35mA / cm 2 The electrolyte was charged for 16 hours at a formation temperature of 43°C. When the initial formation was completed, the density of the electrolyte was 1.290 g / cm 3 ;

[0043] (3) Replenishing electrolyte:

[0044] Inject 10% of the designed mass of the lead-acid battery electrolyte (89g / cell) into the lead-acid battery. The electrolyte has a density of 1.280g / cm 3 of dilute sulfuric acid;

[0045] (4) Final transformation:

[0046] Stage 4: Current density is -5.9mA / cm 2 The current discharges for 3h;

[0047] Stage 5: With a current density of 4.1 mA / cm 2 The current is charged for 11h;

[0048] Stage 6: Current density is 2.4 mA / cm 2 The current is charged for 10h;

[0049] Stage 7: Current density is -4.4mA / cm 2 The current is discharged for 10h;

[0050] Stage 8: With a current density of 6.5 mA / cm 2 The current is charged for 7h;

[0051] Stage 9: With a current density of 4.1 mA / cm 2 The current is charged for 5h;

[0052] Stage 10: Current density is 2.4 mA / cm 2 Charge with current for 12h.

[0053] After the lead-acid battery is formed, measure the battery α-PbO 2 About 35%, the generated particles are larger than α-PbO by electron microscope observation 2 There are many phases, see Figure 1 .

[0054] Example 2

[0055] The formation method for improving the service life of a lead-acid battery comprises the following steps:

[0056] (1) Acid injection:

[0057] Inject 95% of the designed mass of the lead-acid battery electrolyte (845g / cell) into the lead-acid battery. The electrolyte has a density of 1.245g / cm 3 dilute sulfuric acid, and then let the lead-acid battery stand for 1.5 hours. At the end of the standing time, the density of the electrolyte is 1.05g / cm 3 ;

[0058] (2) Initial formation:

[0059] The first stage: the current density is 2.35mA / cm 2 The current is charged for 1.5h, and the formation temperature is 41℃. At this time, α-PbO 2 / β-PbO 2 The ratio of PbSO 4 The content is low;

[0060] The second stage: the current density is 4.1mA / cm 2 The battery is charged with a current of 24 hours, the formation temperature is 48℃, and the battery terminal voltage reaches 2.82V. At this time, part of PbSO4 is converted into β-PbO 2 ;

[0061] The third stage: the current density is 2.35mA / cm 2 The current was charged for 16 hours at a formation temperature of 42°C. When the initial formation was completed, the density of the electrolyte was 1.287 g / cm 3 ;

[0062] (3) Replenishing electrolyte:

[0063] Inject 5% of the designed mass of the lead-acid battery electrolyte (44g / cell) into the lead-acid battery. The electrolyte has a density of 1.280g / cm 3 of dilute sulfuric acid;

[0064] (4) Final transformation:

[0065] Stage 4: Current density is -5.9mA / cm 2 The current discharges for 3h;

[0066] Stage 5: With a current density of 4.1 mA / cm 2 The current is charged for 11h;

[0067] Stage 6: Current density is 2.4 mA / cm 2 The current is charged for 10h;

[0068] Stage 7: Current density is -4.4mA / cm 2 The current is discharged for 10h;

[0069] Stage 8: Current density is 6.5 mA / cm 2 The current is charged for 7h;

[0070] Stage 9: With a current density of 4.1 mA / cm 2 The current is charged for 5h;

[0071] Stage 10: Current density is 2.4 mA / cm 2 Charge with current for 12h.

[0072] After the lead-acid battery is formed, measure the battery α-PbO 2 About 36%, the generated particles are larger than α-PbO by electron microscope observation. 2 There are many physical phases.

[0073] Comparative Example 1

[0074] The conventional formation method for increasing the service life of lead-acid batteries comprises the following steps:

[0075] (1) Acid injection:

[0076] Inject 100% of the designed mass of the electrolyte of the lead-acid battery (889g / cell) into the lead-acid battery. The electrolyte has a density of 1.275g / cm 3 dilute sulfuric acid, and then let the lead-acid battery stand for 1.5 hours. At the end of the standing time, the density of the electrolyte is 1.039g / cm 3 ;

[0077] (2) Initial formation:

[0078] The first stage: the current density is 2.35mA / cm 2 The current is charged for 1.5h, and the formation temperature is 45℃. At this time, α-PbO 2 / β-PbO 2 The ratio of PbSO 4 The content is about 50%;

[0079] The second stage: the current density is 4.1mA / cm 2 The battery is charged for 24 hours at a formation temperature of 54°C and the terminal voltage reaches 2.82V. At this time, part of the PbSO 4 Conversion to β-PbO 2 ;

[0080] The third stage: the current density is 2.35mA / cm 2 The electrolyte was charged for 16 hours at a formation temperature of 47°C. When the initial formation was completed, the density of the electrolyte was 1.302 g / cm 3 ;

[0081] (3) Replenishing electrolyte:

[0082] Because it is a comparative example, 100% of the designed electrolyte mass has been added when acid injection begins, so there is no need to inject acid;

[0083] (4) Final transformation:

[0084] Stage 4: Current density is -5.9mA / cm 2 The current discharges for 3h;

[0085] Stage 5: With a current density of 4.1 mA / cm 2 The current is charged for 11h;

[0086] Stage 6: Current density is 2.4 mA / cm 2 The current is charged for 10h;

[0087] Stage 7: Current density is -4.4mA / cm 2 The current is discharged for 10h;

[0088] Stage 8: With a current density of 6.5 mA / cm 2 The current is charged for 7h;

[0089] Stage 9: With a current density of 4.1 mA / cm 2 The current is charged for 5h;

[0090] Stage 10: Current density is 2.4 mA / cm 2 Charge with current for 12h.

[0091] After the lead-acid battery is formed, measure the battery α-PbO 2 About 8%, the generated particles are smaller than β-PbO by electron microscope observation 2 There are many phases, see Figure 2 .

[0092] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A formation method for improving the service life of a lead-acid battery, characterized in that: The following steps are involved: (1) Acid injection: Inject 90%-95% of the designed mass of the electrolyte of the lead-acid battery into the lead-acid battery. The electrolyte has a density of 1.240-1.260g / cm 3 dilute sulfuric acid, and then let the lead-acid battery stand for 1-2 hours. At the end of the standing time, the density of the electrolyte is 1.05±0.025g / cm 3 ; (2) Initial formation: The first stage: the current density is 2-4mA / cm 2 The current is charged for 1-3h, and the formation temperature is 35-45℃; The second stage: the current density is 3-5mA / cm 2 The battery is charged with a current of 20-27 hours, the formation temperature is 40-50℃, and the battery terminal voltage reaches 2.70-2.90V; The third stage: the current density is 2-4mA / cm 2 The current is charged for 10-17h, the formation temperature is 35-45℃, and the density of the electrolyte is 1.265-1.290g / cm 3 ; (3) Replenishing electrolyte: Inject 5%-10% of the designed mass of the electrolyte of the lead-acid battery into the lead-acid battery. The electrolyte has a density of 1.265-1.290g / cm 3 of dilute sulfuric acid; (4) Final transformation: The fourth stage: the current density is -4~-8mA / cm 2 The current discharge is 2-4h; The fifth stage: the current density is 3-5mA / cm 2 The current is charged for 8-12h; Stage 6: Current density is 2-4 mA / cm 2 The current is charged for 10-14h; The seventh stage: the current density is -3~-6mA / cm 2 The current discharge is 8-12h; Stage 8: Current density is 4-8mA / cm 2 The current is charged for 5-8h; The ninth stage: with a current density of 3-5 mA / cm 2 The current is charged for 3-5h; Stage 10: Current density of 2-4 mA / cm 2 The current is charged for 10-14h.

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