Lead-acid battery acid adding and formation apparatus and method

Abstract

The application discloses a lead storage battery acid adding and formation equipment, which comprises a vacuum system and an acid pot, the acid pot is provided with an acid adding nozzle and a lower acid nozzle, the vacuum system comprises a first gas storage tank and an air compressor for vacuumizing the first gas storage tank, a plurality of acid adding pipes are circumferentially arranged on the tank wall of the first gas storage tank, and the acid adding pipes are uniformly and interval arranged in a circular ring shape; the acid adding pipe comprises a main pipe and branch pipes connected with the main pipe and the first gas storage tank at two ends respectively; the top end of the main pipe is used as an acid adding opening, the bottom end is connected with the acid adding nozzle of the acid pot, a first valve for opening and closing the acid adding opening is arranged above the position where the branch pipe is connected with the main pipe on the main pipe, and a second valve for air flow on-off is arranged on the branch pipe; the application discloses a lead storage battery acid adding and formation method. The annular arrangement design solves the problem that the environmental temperature of the edge battery is inconsistent in the vacuum formation process of the linear type or multiple linear type arrangement, thereby causing the poor consistency of the same road battery.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of vacuum formation of lead storage batteries, in particular to a lead storage battery acid adding and formation device and method. BACKGROUND

[0002] The formation process of lead storage batteries has undergone a process from external formation to internal formation, and the internal formation process now mainly adopts battery internal formation (referred to as pool internal formation) and acid circulation. In the AGM valve-regulated lead storage battery, the soft characteristics of the AGM separator result in that the battery cannot be formed by the acid circulation type of fast and time-saving formation. In the past ten years, the lead storage batteries using AGM separators in China have been formed by internal formation regardless of the use for energy storage, power, automobile starting or standby power supply, and the low current density of the formation process of the lead battery internal formation has resulted in low production efficiency, long production cycle, large open formation acid mist and other phenomena, which have not been improved by the process and production equipment, that is, there has been no great progress in the formation process of lead storage batteries in the past ten years. In the internal formation aspect, some manufacturers have also been researching vacuum formation processes in recent years, and have achieved certain results while encountering some difficulties, for example: in the production process of the battery, the heat generated in the formation of the battery mainly comes from two aspects: 1. The main substances of the solidified positive plate are PbO, PbSO4, 1BS, 3BS, 4BS and a small amount of lead, among which PbO and basic lead sulfate are basic compounds, so in the formation process, they will react with sulfuric acid in the electrolyte and generate a large amount of heat, which will diffuse from the inside of the battery to the outside; 2. The current value in the vacuum formation process affects the formation efficiency, and the current value also affects the battery formation temperature. In the battery formation process, the Joule heat formed due to the internal resistance Rint (including ohmic resistance and polarization resistance Rf) of the battery is Q = I 2 RT. Often, technicians want to increase the current value to accelerate the formation of the battery through vacuum formation (often, the current in the normal pressure formation process does not exceed 0.3C, while in the vacuum formation process, the process current can reach 0.6C at the maximum), but increasing the formation current will also generate more heat in the battery.

[0003] The heat generated by the above two methods is removed by the negative pressure in the vacuum formation process. The biggest advantage of vacuum formation is that the heat generated in the formation process is removed by vacuum negative pressure, which is conducive to the use of larger formation current for formation, thereby shortening the formation time, which can be shortened from the current 2-3 days to about 1 day. The reduction of the charging capacity brings considerable economic benefits, and the charging capacity can be reduced from 9-10C in the normal pressure formation to about 7-8C, and the net charging capacity can be reduced to 5-6C.

[0004] But the lead-acid battery with AGM separator is under a high assembly pressure (usually 40-90 kpa) in the plastic shell, and the heat in the battery is only dissipated through the acid injection nozzle and the ABS plastic shell, and the heat dissipation efficiency is extremely low. The heat generated during the formation process mainly spreads heat through thermal radiation in the near-vacuum environment (there are three ways to transfer heat: conduction, convection and thermal radiation), and it is difficult for the heat generated inside the battery to dissipate.

[0005] The boiling point of dilute sulfuric acid used as electrolyte in the battery is different at different air pressures, see "Chemical Engineering Property Calculation Chart Manual" pages 296 and 315, and a lower negative pressure value is not enough to make the electrolyte boil, so a very high negative pressure value is needed to make the electrolyte boil. A reasonable negative pressure value will lower the boiling point of the electrolyte in the battery and the formation acid pot to 38-45℃, and a reasonable vacuum formation process can make the temperature of the electrolyte in the battery during the vacuum formation process exceed 43 degrees but not higher than 55 degrees, and the water vapor generated by boiling is continuously removed by the negative pressure, while a large amount of heat generated by the increased current during the formation process is also removed. A reasonable vacuum formation process and vacuum formation equipment can ensure that the temperature in the battery is within the optimal process temperature range (25-55℃), and can also prevent the heat generated by the increased current in the battery from not being removed in time, causing thermal runaway.

[0006] The heat dissipation of each battery during the vacuum formation process causes the temperature of the battery to be affected by the surrounding batteries, resulting in inconsistent temperatures, which affects the formation efficiency of the battery. As shown in Figure 1 , the batteries are placed in series and parallel for vacuum formation, and the heat generated by the batteries during the formation process spreads to the surrounding batteries, directly affecting the temperature of the surrounding batteries, and the temperature of the battery during the formation process affects the efficiency of the battery and the conversion degree of different substances in the battery plate. The two end batteries in a row of formed batteries have a lower temperature than the other batteries in the same row during the vacuum formation process, so the temperature of the two end batteries is lower than that of the other batteries in the same row, which affects the evaporation of the electrolyte in the battery during the vacuum process, resulting in a lower electrolyte density than the other batteries in the same row during the formation process, which leads to a lower formation efficiency than the other batteries in the same row, and the formation voltage value is also lower than the other batteries in the same row, which affects the water loss and the electrolyte density during the formation process, resulting in poor consistency of the formation, which has been verified by experiments, as shown in Figure 1 , the temperature of the two end batteries 1# and 18# during the formation process is lower than that of the other batteries in the same row, and the capacity of the batteries 1# and 18# is about 5% lower than that of the other batteries in the same row, and the electrolyte density in the battery is 0.05-0.08 g / cm 3 , the temperature of the two end batteries in the same row during the vacuum formation process is lower, and the electrolyte density and capacity after formation are lower, and this phenomenon is repeated after many experiments. SUMMARY

[0007] An object of the present application is to provide a lead-acid battery acid adding and formation device, which arranges one row of batteries in a ring shape to ensure equal spacing between each battery in the same row, thereby avoiding the situation that one row of batteries or multiple rows of vacuum-formed batteries are arranged in a "two-end" manner due to linear arrangement, and thus avoiding the situation that the two-end batteries are affected by inconsistent formation temperature of surrounding batteries, thereby affecting the formation efficiency and formation result.

[0008] The lead-acid battery acid adding and formation device comprises a vacuum system and an acid pot, the acid pot is provided with an acid adding nozzle and a lower acid nozzle, the vacuum system comprises a first gas storage tank and an air compressor for vacuumizing the first gas storage tank, the tank wall of the first gas storage tank is circumferentially provided with a plurality of acid adding pipes, and each acid adding pipe is arranged in a circular ring shape and uniformly spaced; the acid adding pipe comprises a main pipe and branch pipes connected to the main pipe and the first gas storage tank at two ends; the top end of the main pipe serves as an acid adding port, and the bottom end is connected to the acid adding nozzle of the acid pot; a first valve for opening and closing the acid adding port is arranged above the position where the branch pipe is connected to the main pipe, and a second valve for air flow on-off is arranged on the branch pipe.

[0009] In the present scheme, the acid adding pipe is arranged in a ring shape, and when the battery is vacuum-formed, the semi-finished battery is also arranged in a ring shape, thereby avoiding the situation that one row of batteries or multiple rows of vacuum-formed batteries are arranged in a "two-end" manner due to linear arrangement, and thus avoiding the situation that the two-end batteries are affected by inconsistent formation temperature of surrounding batteries, thereby affecting the formation efficiency and formation result.

[0010] Preferably, the acid adding pipe and the first gas storage tank are made of 316 stainless steel and are integrally formed, the acid adding pipe is in T shape and combined with the first gas storage tank, and the upper part of the acid adding pipe is in a funnel shape to facilitate the pouring of electrolyte. Both the first valve and the second valve are electromagnetic valves, the first valve is opened when adding acid and closed at other times, and the second valve is closed when adding acid and opened at other times.

[0011] Preferably, the bottom end of the acid adding pipe is connected to an acid-resistant hose in communication therewith, the bottom end of the acid-resistant hose is provided with a PVC lower acid nozzle, and the PVC lower acid nozzle is connected to the acid adding nozzle of the acid pot through a first base. Preferably, the acid-resistant hose is made of acid-resistant rubber hose.

[0012] In the present scheme, the acid-resistant rubber hose is slightly curved in length to ensure that the first base wrapping the PVC lower acid nozzle is completely attached to the acid pot without being limited by the length of the connecting pipe.

[0013] Further preferably, the two ends of the first base wrap the PVC lower acid nozzle and the acid adding nozzle of the acid pot respectively, and the inner diameter of the end of the first base corresponding to the acid adding nozzle of the acid pot is smaller than the outer diameter of the acid adding nozzle of the acid pot.

[0014] In the scheme, the first base can tightly wrap the acid pot acid injection nozzle, to ensure that the acid is not leaked, and when vacuuming, through the negative pressure can make the first base and the acid injection nozzle tightly fit, no gas leakage.

[0015] As preferred, the lower acid nozzle of the acid pot is provided with a second base for connecting with the semi-finished battery acid injection nozzle; further preferably, the first base and the second base are both rubber bases.

[0016] As preferred, it also includes a circular workbench, the first gas tank is arranged on the circular workbench, and the circular workbench is provided with a limiting groove for placing the semi-finished battery at a position corresponding to each acid injection pipe, and the limiting grooves are also circularly and uniformly arranged.

[0017] In the scheme, the limiting grooves are also circularly arranged to ensure that each battery has equal spacing with other surrounding batteries, and also facilitate the placement of the batteries.

[0018] As preferred, the vacuum system further includes a filter tank arranged on the pipeline between the first gas tank and the air compressor, close to the first gas tank, and a second gas tank close to the air compressor, and a third valve, a fourth valve and a fifth valve are arranged on the pipeline between the first gas tank and the filter tank, on the pipeline between the filter tank and the second gas tank, and on the pipeline between the second gas tank and the air compressor, respectively.

[0019] Further preferably, the volume of the second gas tank is 5-8 times the volume of the first gas tank.

[0020] In the scheme, the air compressor is placed in the air compressor cabinet, and the air compressor cabinet has a control operation panel, and the air compressor has a negative pressure range of 0-100kpa. The volume of the second gas tank is 5-8 times larger than the volume of the first gas tank, which serves as a negative pressure temporary storage source and maintains the stability of the negative pressure during the entire vacuum formation process, and the gas tank assists the battery in vacuum formation to provide a negative pressure buffer zone.

[0021] The function of the second gas tank with a volume much larger than that of the first gas tank is: 1. It is equivalent to a warehouse of negative pressure, so that the air compressor is not directly connected to the small-capacity first gas tank, which causes the air compressor to be frequently turned on, which is not conducive to the service life of the air compressor, and the capacity of the first gas tank is necessarily limited due to design; 2. The large-capacity negative pressure reserve is also conducive to providing a macroscopic adjustment and support for the negative pressure required for the formation of the battery, and plays a role in stabilizing the negative pressure of the first gas tank.

[0022] The filter tank plays a role in neutralizing the acid mist generated during the vacuum formation process, avoiding corrosion of the air pressure pump by the acid mist. The third valve, the fourth valve and the fifth valve are also electromagnetic valves.

[0023] Another object of the present application is to provide a lead-acid battery acid adding and formation method using the lead-acid battery acid adding and formation device described above, the method comprising the following steps:

[0024] (1) first connect each semi-finished battery to be acid added and formed to the lower acid nozzle of each acid pot in sequence;

[0025] (2) open the first valve and close the second valve to add acid liquid into each acid pot in a quantitative manner;

[0026] (3) close the first valve and open the second valve to perform negative pressure extraction by the vacuum system, and each semi-finished battery is synchronously acid added in a quantitative manner;

[0027] (4) after acid addition is completed, close the first valve and open the second valve to perform negative pressure extraction by the vacuum system, and each semi-finished battery is synchronously vacuum formed.

[0028] In step (3), when acid is added, after the negative pressure in the gas storage tank reaches the process set value, the second electromagnetic valve is opened, the negative pressure extraction of the semi-finished battery and the electrolyte in the acid pot is started, the negative pressure extraction is stopped after 5-10 seconds, the second electromagnetic valve is closed, the first electromagnetic valve is opened, the electrolyte in the acid pot is poured into the corresponding semi-finished battery, the first electromagnetic valve is closed, the second electromagnetic valve is opened, the negative pressure extraction and acid pouring operation is repeated 3 times under a vacuum degree of-49 to-50 kpa, then the vacuum degree of the air compressor is adjusted to-95 to-99 kpa, the negative pressure extraction and acid pouring operation is performed again 3 times in the same way, the electrolyte is fully poured into the semi-finished battery, and the consistency of the acid immersion time of the battery pole group is ensured, after the electrolyte is poured, the battery is placed for 2 minutes before starting the power formation.

[0029] As a preferred, after acid addition is completed, the process vacuum degree of-95 to-99 kpa is maintained, the battery is placed for at least 2 minutes before starting the power formation.

[0030] As a preferred, the formation step comprises:

[0031] (1) 0.6C charging for 5h in the first stage,

[0032] (2) 15min of standing in the second stage,

[0033] (3) 0.375C discharging for 1h in the third stage,

[0034] (4) 0.6C charging for 40min in the fourth stage,

[0035] (5) 0.45C charging for 3h in the fifth stage,

[0036] (6) 20min of standing in the sixth stage,

[0037] (7) Stage 7 0.375C discharge 1h40min,

[0038] (8) Stage 8 0.45C charge 1h18min,

[0039] (9) Stage 9 0.3C charge 1h30min,

[0040] (10) Stage 10 0.2C charge 1h30min,

[0041] (11) Stage 11 rest 15min,

[0042] (12) Stage 12 0.5C discharge 2h,

[0043] (13) Stage 13 0.5C charge 1h30min,

[0044] (14) Stage 14 0.25C charge 2h,

[0045] (15) Stage 15 0.09C charge 3h, wherein, the vacuum is ended after the first hour, the acid is extracted after the second hour, and the formation is ended after the acid extraction is completed.

[0046] Advantages of the present application:

[0047] 1. Environmental protection advantage brought by vacuum formation. The battery is connected by pipeline throughout the formation process to avoid acid mist leakage during the formation process and eliminate acid mist pollution to the environment during the formation process.

[0048] 2. The design of annular arrangement solves the problem of inconsistent environmental temperature of the edge battery during the vacuum formation process of linear placement or multiple linear placement, thereby causing poor consistency of the same road battery.

[0049] 3. Vacuum formation is carried out at a negative pressure of -95 to -99 kpa, which can reduce the boiling point of electrolyte to 39 to 45℃. A large amount of heat generated during the conversion of active substances during the formation process will be taken away by the water vapor generated by the boiling of electrolyte under negative pressure, ensuring that the temperature of the battery during the formation process will not cause thermal runaway due to large current formation.

[0050] 4. Scientific and reasonable vacuum formation process ensures that the formation time is shortened to about 24h, and the total formation capacity is reduced to 7 to 8C. Compared with the existing formation process, the formation time is shortened by more than 1 day, and the capacity is reduced by more than 2C, greatly creating economic value. The vacuum formation process matches the temperature control in the above formation process to ensure that the battery will not be out of control during the formation process. BRIEF DESCRIPTION OF DRAWINGS

[0051] Figure 1 It is a schematic diagram of the battery in series and parallel in the background art;

[0052] Figure 2 It is a schematic structural diagram of the present invention;

[0053] Figure 3 for Figure 2 An enlarged view of the first gas storage tank;

[0054] Figure 4 The schematic structural diagram of Comparative Example 1;

[0055] Figure 5 Implementation of the method of the present invention into a voltage curve;

[0056] Figure 6 Implementation of the method of the present invention into a temperature curve;

[0057] Figure 7 This is the voltage curve of comparative example 1;

[0058] Figure 8 This is the temperature curve of comparative example 1;

[0059] Figure 9 This is the voltage curve of comparative example 2. DETAILED DESCRIPTION

[0060] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. 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 making creative efforts are within the scope of protection of the present invention.

[0061] Example 1

[0062] like Figure 2 As shown, a lead-acid battery acid addition and formation equipment includes a vacuum system, which includes a first gas storage tank 1 and an air compressor 2. The air compressor 2 is used to evacuate the first gas storage tank 1; a plurality of integrally formed acid injection pipes 3 are arranged in a circumferential array on the tank wall of the first gas storage tank 1. The acid injection pipes 3 are T-shaped and specifically include a main pipe and a branch pipe. A "trumpet-shaped" acid injection port is provided at the top of the main pipe. At the same time, a first solenoid valve 31 is provided on the main pipe above the branch pipe, and a second solenoid valve 32 is provided on the branch pipe.

[0063] Each acid injection pipe 3 is correspondingly provided with an acid pot 4 below. Specifically, the bottom end of the acid injection pipe 3 is connected with an acid-resistant rubber hose 5 which is in communication with the acid injection pipe 3, the bottom end of the acid-resistant rubber hose 5 is provided with a PVC lower acid nozzle 6, the PVC lower acid nozzle 6 is connected with the acid pot acid nozzle through a first rubber base 7; wherein the two ends of the first rubber base 7 respectively wrap the PVC lower acid nozzle 6 and the acid pot acid nozzle, and the end diameter of the first rubber base 7 corresponding to the acid pot acid nozzle is smaller than the outer diameter of the acid pot acid nozzle, so as to ensure the sealing property; in addition, the second rubber base 8 is arranged on the acid pot lower acid nozzle, for connecting with the semi-finished battery acid injection nozzle.

[0064] In the embodiment, the lead-acid battery acid adding and formation device further comprises a circular workbench 9, the first gas tank 1 is arranged on the circular workbench 9, and the circular workbench 9 is provided with limiting grooves 91 corresponding to the positions of the acid injection pipes 3, and the limiting grooves 91 are also arranged in a circular array, so as to ensure that the distance between each battery and other surrounding batteries is equal; in the embodiment, the angle between adjacent limiting grooves 91 is 20°, that is, 18 semi-finished batteries 100 can be placed on the circular workbench 9.

[0065] In the embodiment, the vacuum system further comprises a filter tank 10 arranged on the pipeline between the first gas tank 1 and the air compressor 2 and close to the first gas tank 1, and a second gas tank 11 arranged on the pipeline close to the air compressor 2, and a third electromagnetic valve 12, a fourth electromagnetic valve 13 and a fifth electromagnetic valve 14 are arranged on the pipeline between the first gas tank 1 and the filter tank 10, on the pipeline between the filter tank 10 and the second gas tank 11, and on the pipeline between the second gas tank 11 and the air compressor 2 in sequence.

[0066] A lead-acid battery formation method is adopted in the lead-acid battery acid adding and formation device, and the method is described below by taking a 2V200 lead-acid battery as an example.

[0067] As shown in Figure 2 Fig. 1, 18 semi-finished batteries are placed in the positioning grooves of the circular workbench, the batteries with labels are placed in position, the charging wires and voltage collection wires are connected between the batteries, and the temperature collection wires are also pasted on the same positions outside the batteries; the second rubber base is used to connect the semi-finished battery acid injection nozzle and the acid pot lower acid nozzle.

[0068] After the lower acid pipeline is connected with the semi-finished battery, the second electromagnetic valve is closed, the first electromagnetic valve is opened, 39010±3 g of 1.12-1.20 g / cm3 dilute sulfuric acid electrolyte is injected into the semi-finished battery through the upper end of the acid injection pipe; after the acid injection of 18 semi-finished batteries is completed, the electrolyte is temporarily stored in the acid pot under the pressure of the gas pressure in the battery, which is beneficial to the next step of simultaneously injecting electrolyte into the acid pot and ensures the consistency of the acid immersion time of the electrode group; the first electromagnetic valve and the first electromagnetic valve are closed, the third, fourth and fifth electromagnetic valves are opened, the first gas storage tank, the filter tank, the second gas storage tank, the air compressor and the pipeline form a passage, the air compressor vacuum degree is set to-49 to-50 kpa, the air compressor cabinet switch in the vacuum system is opened, and the vacuum pump starts to work to draw negative pressure in the first gas storage tank and the second gas storage tank.

[0069] After the negative pressure in the gas storage tank reaches the process set value, the second electromagnetic valve is opened, the electrolyte in the semi-finished battery and the acid pot is drawn to negative pressure, and the negative pressure is stopped after 5-10 seconds, the second electromagnetic valve is closed, the first electromagnetic valve is opened, the electrolyte in the acid pot is injected into the corresponding semi-finished battery, and then the first electromagnetic valve is closed, the second electromagnetic valve is opened, and the vacuum degree is-49 to-50 kpa, the negative pressure and acid injection operation is repeated 3 times; then the air compressor vacuum degree is adjusted to-95 to-99 kpa, and the negative pressure and acid injection operation is performed again 3 times according to the same method, so that the electrolyte is fully injected into the semi-finished battery, and the consistency of the acid immersion time of the battery electrode group is ensured, and after the electrolyte is injected, the electrolyte is placed for 2 minutes before being electrified.

[0070] The role of standing still and continuously drawing vacuum for 2 minutes before electrification is: through the test research of the inventor, after the vacuum degree and the acid injection mode in the foregoing are passed, the temperature outside the battery tends to be stable after standing still for 2 minutes, the PbSO4 content of the anode plate in the battery is no longer increased and tends to be balanced, which achieves the effect of standing still for 1 h after acid injection, i.e. the PbSO4 content value after acid immersion for 1 h is approximately the same as that in the normal pressure formation mode.

[0071] The formation process is as follows:

[0072] After standing for 2 min, the formation was started, the 1st stage was 120 A (0.6 C) charging for 5 h, the 2nd stage was standing for 15 min, the 3rd stage was 75 A (0.375 C) discharging for 1 h, the 4th stage was 120 A (0.6 C) charging for 40 min, the 5th stage was 90 A (0.45 C) charging for 3 h, the 6th stage was standing for 20 min, the 7th stage was 75 A (0.375 C) discharging for 1 h 40 min, the 8th stage was 90 A (0.45 C) charging for 1 h 18 min, the 9th stage was 60 A (0.3 C) charging for 1 h 30 min, the 10th stage was 40 A (0.2 C) charging for 1 h 30 min, the 11th stage was standing for 15 min, the 12th stage was 100 A (0.5 C) discharging for 2 h, the 13th stage was 100 A (0.5 C) charging for 1 h 30 min, the 14th stage was 50 A (0.25 C) charging for 2 h, and the 15th stage was 18 A (0.09 C) charging for 3 h, wherein the vacuum was ended after the first hour, after the second hour, the second electromagnetic valve was closed, the first electromagnetic valve was opened, the acid pot was removed, and the normal pressure was restored for acid extraction, after the acid extraction was completed, the formation was ended, the total time was 24 h, the total charging amount was 1521 (7.6 C) ah, and the net charging amount was 1121 (5.6 C) ah.

[0073] The formation voltage curve is shown in Figure 5 The voltage of 1#, 6#, 14# and 18# is collected, and the highest voltage of all the batteries in the formation process does not exceed 2.83 V, which meets the process formation voltage range.

[0074] The formation temperature curve is shown in Figure 6 During the entire formation process, the temperature of the 4 batteries collected in the formation process is consistent, the temperature curves are basically coincided, and the formation temperature range is also within the reasonable range of formation (25-55 ℃, the vacuum is stopped at the end of acid extraction, and the battery temperature rises).

[0075] The water loss is as shown in Table 1:

[0076] Table 1

[0077]

[0078] The water loss value of the center of the 18 batteries in the formation process is 1617 g ± 6, and the water loss in the formation process is consistent.

[0079] The formation results are as follows:

[0080] After analyzing the batteries after formation, the positive and negative plates are analyzed in terms of “upper region”, “middle region” and “lower region” and “XRD” analysis.

[0081] The positive plate analysis is as shown in Table 2:

[0082] Table 2

[0083]

[0084] The negative plate was analyzed as shown in Table 3:

[0085] Table 3

[0086]

[0087] The chemical analysis method is basically consistent with the XRD analysis of PbO2 and PbSO4, and the values have certain errors due to different analysis methods. According to the results, the positive PbO2 content, phase analysis, α-PbO2 / β-PbO2 content ratio, and negative plate PbSO4 content all meet the process requirements.

[0088] The open circuit voltage is as shown in Table 4:

[0089] Table 4

[0090] Position 1 2 3 4 5 6 7 8 9 Open circuit voltage 2.19V 2.20V 2.19V 2.19V 2.20V 2.19V 2.20V 2.20V 2.19V Position 10 11 12 13 14 15 16 17 18 Open circuit voltage 2.19V 2.19V 2.20V 2.19V 2.20V 2.20V 2.20V 2.19V 2.20V

[0091] The open circuit voltage: the open circuit voltage range is 2.19V-2.20V, and the open circuit voltage consistency is good.

[0092] After formation, the positive plate PbO2 content is greater than 88%, the negative PbSO4 is less than 8%, and according to the phase analysis of the plate, the α-PbO2 / β-PbO2 ratio is greater than 0.4 (according to Dr. Pavlov's theoretical analysis, the α-PbO2 / β-PbO2 ratio of the positive plate after formation is greater than 0.4, which is a basis for long-life batteries). The negative plate lead sulfate content is less than 8%.

[0093] The formation process system of the present application is the optimal scheme obtained by the inventor through a large number of process experiments. After each charging process, the battery formation temperature or voltage rises too fast when the current value and time exceed the above process (the voltage value during the formation process does not exceed 2.84V / single cell, otherwise more electric quantity is charged to perform the electrolysis of water side reaction, rather than the conversion of active material in the battery, and the temperature in the battery will rise to 60℃ or even higher), which does not achieve the effect of rapid formation and reasonable temperature range. After each charging, the battery is discharged, which on the one hand reduces the temperature of the battery during the formation process, and on the other hand improves the charging acceptance ability, increases the conversion of active material, and effectively shortens the battery formation time.

[0094] Comparative Example 1:

[0095] Similarly, taking a 2V200 lead-acid battery as an example, as shown in Table 5: Figure 3As shown, the square workbench is divided into two columns, and there are 18 battery positioning slots, 9 in each row, and the two rows of positioning slots are evenly arranged on both sides of the first air cylinder. 18 semi-finished batteries are placed in each positioning slot. After the labeled batteries are in place, the charging wires and voltage collection wires are connected between the batteries, and the temperature collection wires are also pasted on the outside of the batteries; the finished battery acid nozzle is connected to the acid nozzle below the acid pot using a second rubber base.

[0096] After the lower acid pipeline is connected to the semi-finished battery, the second electromagnetic valve is closed, the first electromagnetic valve is opened, and 1.12-1.20 g / cm3 dilute sulfuric acid electrolyte 4230±5 g is poured into the semi-finished battery through the acid injection port at the upper end of the acid injection pipeline; after the acid is added to the 18 semi-finished batteries, the electrolyte is subjected to the pressure of the gas pressure in the battery, and is temporarily stored in the acid pot, which is beneficial to the next step of simultaneously pouring electrolyte into the acid pot, ensuring the consistency of the acid immersion time of the electrode group; the first electromagnetic valve and the first electromagnetic valve are closed, and the third, fourth, and fifth electromagnetic valves are opened, forming a path for the first air tank, the filter tank, the second air tank, the air compressor, and the pipeline. The air compressor vacuum degree is set to -49 to -50 kpa, and the air compressor cabinet switch in the vacuum system is opened, so that the vacuum pump starts to work and draws negative pressure from the first air tank and the second air tank.

[0097] After the negative pressure in the air tank reaches the process set value, the second electromagnetic valve is opened, and the electrolyte in the semi-finished battery and the acid pot is drawn under negative pressure; after 5-10 seconds, the negative pressure is stopped, the second electromagnetic valve is closed, and the first electromagnetic valve is opened, so that the electrolyte in the acid pot is poured into the corresponding semi-finished battery; then the first electromagnetic valve is closed, the second electromagnetic valve is opened, and the vacuum degree is -49 to -50 kpa, the above operation is repeated 3 times; then the air compressor vacuum degree is adjusted to -95 to -99 kpa, and the above operation is repeated 3 times, so that the electrolyte is fully poured into the semi-finished battery, and the consistency of the acid immersion time of the battery electrode group is ensured. After the electrolyte is poured, it is placed for 2 minutes before being subjected to the electrochemical formation.

[0098] The formation process is as follows:

[0099] After standing for 2 min, start formation, 1st stage 120A charging for 2 h, 2nd stage standing for 10 min, 3rd stage 120A charging for 2 h, 4th stage standing for 10 min, 5th stage 120A charging for 2 h, 6th stage standing for 10 min, 7th stage 120A charging for 2 min, 8th stage standing for 10 min, 9th stage 100A charging for 2 h, 10th stage standing for 10 min, 11th stage 70A charging for 5 h, 12th stage standing for 30 min, 13th stage 100A discharging for 2 h or single voltage is lower than 1.75 V, 14th stage 100A charging for 1 h 30 min, 15th stage 50A charging for 2 h, 16th stage 18A charging for acid extraction, 2nd hour stop vacuum, close the second electromagnetic valve, open the first electromagnetic valve A, remove the acid pot, restore normal pressure to extract acid, after acid extraction is completed, formation is finished, total time is 24 h, total charging amount is 1996 Ah, and net charging amount is 1796 Ah.

[0100] The formation voltage curve is shown in Figure 7 During the formation process, the 18# battery at the edge of the same row and the 14# battery at the middle area of the same row are affected by temperature, which affects the formation efficiency, so under the same formation process, the formation curve deviates, and the formation efficiency of the 14# battery at the middle area is slightly higher. Moreover, the process uses 0.6C formation current for a long time, which causes the voltage to be too high during the formation process, and the temperature and water loss during the formation process are too large.

[0101] The formation temperature curve is shown in Figure 8 During the formation process, the 18# battery at the edge of the same row and the 14# battery at the middle area of the same row have a temperature difference of about 5℃, whether the surface temperature of the battery is detected or the temperature of the corresponding acid pot is detected, there is a temperature difference, and the temperature difference will cause differences in evaporation, electrolyte density, formation efficiency and other aspects during the formation process, which is not conducive to formation.

[0102] The water loss is as shown in Table 5:

[0103] Table 5

[0104]

[0105] From the water loss, the water loss of the 1#, 9#, 10# and 18# batteries at both ends of the two rows is obviously lower than that of the other batteries in the same row, and the cause and background technology have been analyzed, which will not be described here. Except for 1#, 9#, 10# and 18#, the water loss of the remaining 14 batteries is 2091±24 g, which is larger than the water loss amount of the inventive example, and is also related to the design of the formation process.

[0106] The formation results are as follows:

[0107] The battery after formation was analyzed, and the positive and negative electrode plates were analyzed by XRD according to the "upper region", "middle region" and "lower region".

[0108] The positive electrode plate was analyzed as shown in Table 6.

[0109] Table 6

[0110]

[0111]

[0112] The negative electrode plate was analyzed as shown in Table 7.

[0113] Table 7

[0114]

[0115] The difference in the temperature of different batteries during formation does not affect the proportion of lead dioxide crystal, the content ratio of α-PbO2 / β-PbO2 and the conversion of negative electrode sponge lead.

[0116] The open circuit voltage is shown in Table 8.

[0117] Table 8

[0118] Position 1 2 3 4 5 6 7 8 9 Open circuit voltage 2.23V 2.26V 2.26V 2.25V 2.26V 2.25V 2.25V 2.25V 2.23V Position 10 11 12 13 14 15 16 17 18 Open circuit voltage 2.22V 2.25V 2.26V 2.25V 2.25V 2.25V 2.25V 2.25V 2.23V

[0119] Due to the influence of water loss, the open circuit voltage of the battery is high, and the electrolyte density in the battery is also high. The high open circuit voltage is not conducive to the long-life cycle of the battery, and the voltage of the batteries at both ends of the two paths 1#, 9#, 10# and 18# is 0.02V-0.03V lower than that of other batteries in the same path. The placement method of the battery in Comparative Example 1 is not conducive to the consistency of the vacuum formation battery.

[0120] Comparative Example 2

[0121] Compared with the embodiment of the application, only a different formation process is used, and the formation process is as follows:

[0122] After standing for 2 min, the formation was started, 1st stage 120 A charging for 5 h, 2nd stage 75 A discharging for 1 h, 3rd stage 120 A charging for 4.5 h, 4th stage standing for 15 min, 5th stage 75 A discharging for 1 h 40 min, 6th stage 100 A charging for 2 h, 7th stage 70 A charging for 3 h, 8th stage 50 A charging for 3 h, 9th stage standing for 15 min, 10th stage 100 A discharging for 2 h, 11th stage 100 Ah charging for 1.5 h, 12th stage 50 A discharging for 2 h, 13th stage 100 A charging for 1 h 30 min, 14th stage 50 A charging for 2 h, 15th stage 18 A charging for 3 h, the vacuum was stopped at the 2nd hour, the second electromagnetic valve was closed, the first electromagnetic valve was opened, the acid pot was removed, and the normal pressure was restored to perform the acid extraction, after the acid extraction was completed, the formation was ended, the total time was 24 h, the total charging capacity was 1986 Ah, the net charging capacity was 1585 Ah, and the charging time was 28 h.

[0123] The formation voltage curve is shown in Figure 9

[0124] Compared with the embodiment of the application, the charging capacity is more by 466 Ah, the net charging capacity is more by 464 Ah, the charging time is more by 4 h, the charging voltage appears a clear high voltage region of 2.83-2.87 V, and the electric quantity charged in the high voltage region is mostly consumed by the "side reaction" of electrolytic water, which has little effect on the formation conversion of the battery, and the electrolytic water is more likely to cause the inconsistency of the electrolyte density after the formation.

[0125] The same arrangement is adopted in Comparative Example 2 and the embodiment of the application, so the temperature difference of the battery in the formation process is very small, which is not listed in Comparative Example 2.

[0126] The water loss is as shown in Table 9:

[0127] Table 9

[0128] Position 1 2 3 4 5 6 7 8 9 Water loss 1820g 1807g 1800g 1838g 1853g 1832g 1847g 1808g 1810g Position 10 11 12 13 14 15 16 17 18 Water loss 1797g 1820g 1795g 1815g 1803g 1803g 1798g 1823g 1818g

[0129] The water loss value of the center of 18 batteries in the formation process is 1816 g ± 22 g, which is more than that of the embodiment of the application by 199 g on average, and the water loss consistency is poorer than that of the embodiment of the application.

[0130] The formation results are as follows:

[0131] After the formation, the positive and negative plates are analyzed in terms of the "upper region", "middle region" and "lower region" for physical and chemical analysis and "XRD" analysis.

[0132] The positive plate analysis is as shown in Table 10:

[0133] Table 10

[0134] ​

[0135] The negative plate was analyzed as shown in Table 11:

[0136] Table 11

[0137]

[0138]

[0139] The chemical analysis method is basically consistent with the XRD analysis of the total amount of PbO2 and PbSO4, and there is a certain error in the numerical value due to different analysis methods. The PbO2 content of the positive plate meets the formation requirement, and the lead sulfate content of the negative electrode is relatively high. According to Dr. Pavlov's theoretical analysis, the formation current and the electrolyte density during the formation process will affect the α-PbO2 / β-PbO2 content ratio.

[0140] The open circuit voltage is as shown in Table 12:

[0141] Table 12

[0142] Position 1 2 3 4 5 6 7 8 9 Open circuit voltage 2.21V 2.21V 2.20V 2.12V 2.22V 2.22V 2.22V 2.21V 2.21V Position 10 11 12 13 14 15 16 17 18 Open circuit voltage 2.20V 2.21V 2.19V 2.20V 2.20V 2.20V 2.20V 2.21V 2.21V

[0143] The open circuit voltage: the open circuit voltage range is 2.19V-2.22V, and the consistency of the open circuit voltage is poorer than that of the embodiment of the application, which is affected by the high water loss during the formation process. The open circuit voltage is proportional to the electrolyte density in the battery, and high electrolyte density is not conducive to the long-life cycle of the battery.

[0144] Through comparison of the embodiment of the application and the comparative example, it is not difficult to find that:

[0145] 1. During the formation process of the same road battery, the "head and tail" situation occurs, and the batteries at the head and tail are affected by temperature, which will affect the evaporation amount of the electrolyte during the vacuum formation process, thereby causing a large difference in water loss between the batteries at the head and tail and the batteries outside the head and tail, thereby causing a difference in electrolyte density, affecting the consistency of the battery and the battery cycle.

[0146] 2. With the same battery arrangement, the use of different formation processes affects the battery, and the higher the charging rate, the more likely it is to cause a difference in water loss, thereby causing a difference in the consistency of the electrolyte density.

[0147] 3. Long time and high charging current for formation are not conducive to the improvement of the α-PbO2 / β-PbO2 content ratio of the positive plate, and the excess of the electric quantity does not have economic efficiency.

[0148] 4. The net charging capacity of 5.5C can complete the formation of the lead-acid battery plate and meet the process requirements under the cooperation of reasonable formation process.

[0149] Although the present application has been described in detail with reference to the foregoing embodiments, the technical solutions recorded in the foregoing embodiments can be modified, or some of the technical features can be replaced by equivalent features, by those skilled in the art, any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A lead-acid battery acid adding and formation apparatus comprising a vacuum system and an acid pot having an acid adding nozzle and a lower acid nozzle, characterized in that, The vacuum system comprises a first gas tank and an air compressor for vacuumizing the first gas tank, the tank wall of the first gas tank is circumferentially provided with a plurality of acid injection pipes, each of the acid injection pipes is uniformly and circularly spaced; the acid injection pipe comprises a main pipe and branch pipes respectively connected with the main pipe and the first gas tank at two ends; the top end of the main pipe serves as an acid injection port, and the bottom end is connected with an acid injection nozzle of an acid pot; a first valve for opening and closing the acid injection port is arranged on the main pipe above the position connected with the branch pipe, and a second valve for air flow on-off is arranged on the branch pipe.

2. The lead storage battery acid adding and formation apparatus according to claim 1, characterized in that, The bottom end of the acid injection pipe is connected with an acid-resistant hose in communication therewith, the bottom end of the acid-resistant hose is provided with a PVC lower acid nozzle, and the PVC lower acid nozzle is connected with the acid injection nozzle of the acid pot through a first base.

3. The lead storage battery acid adding and formation apparatus according to claim 2, characterized in that, The two ends of the first base wrap the PVC lower acid nozzle and the acid injection nozzle of the acid pot respectively, and the inner diameter of the end of the first base corresponding to the acid injection nozzle of the acid pot is smaller than the outer diameter of the acid injection nozzle of the acid pot.

4. The lead storage battery acid adding and formation apparatus according to claim 1, characterized by The lower acid nozzle of the acid pot is provided with a second base for connecting with the acid injection nozzle of the semi-finished battery.

5. The lead storage battery acid adding and formation apparatus according to claim 1, wherein It also comprises a circular workbench, the first gas tank is arranged on the circular workbench, and a limiting groove for placing the semi-finished battery is arranged on the circular workbench at a position corresponding to each acid injection pipe, and the limiting groove is also uniformly and circularly spaced.

6. The lead storage battery acid adding and formation apparatus according to claim 1, wherein The vacuum system further comprises a filter tank arranged on the pipeline between the first gas tank and the air compressor and close to the first gas tank, and a second gas tank close to the air compressor, and a third valve, a fourth valve and a fifth valve are arranged in sequence on the pipeline between the first gas tank and the filter tank, on the pipeline between the filter tank and the second gas tank, and on the pipeline between the second gas tank and the air compressor.

7. The lead storage battery acid adding and formation apparatus according to claim 6, characterized in that, The volume of the second gas tank is 5-8 times the volume of the first gas tank.

8. A method of acid adding and formation of a lead storage battery, characterized by, The lead storage battery acid adding and formation equipment and method of any one of claims 1-7 comprises the following steps: (1) first, connect each semi-finished battery to be acid added and formed with the lower acid nozzle of each acid pot in sequence; (2) open the first valve and close the second valve, and add a certain amount of acid liquid into each acid pot; (3) close the first valve and open the second valve, perform negative pressure extraction by the vacuum system, then close the second valve, open the first valve, and simultaneously add a certain amount of acid to each semi-finished battery; (4) after the acid adding is completed, close the first valve, open the second valve, perform negative pressure extraction by the vacuum system, and simultaneously form each semi-finished battery in vacuum.

9. The method of claim 8, wherein the lead storage battery is filled with acid and formed. After the acid adding is completed, maintain a process vacuum degree of-95 to-99 kpa, and start the power formation after standing for at least 2 minutes.

10. The method of claim 8, wherein the lead storage battery is filled with acid and formed. The formation step comprises: (1) 0.6C charging for 5h in the first stage, (2) standing for 15min in the second stage, (3) 0.375C discharging for 1h in the third stage, (4) 0.6C charging for 40min in the fourth stage, (5) 0.45C charging for 3h in the fifth stage, (6) standing for 20min in the sixth stage, (7) 0.375C discharging for 1h40min in the seventh stage, (8) 0.45C charging for 1h18min in the eighth stage, (9) 0.3C charging for 1h30min in the ninth stage, (10) Stage 10 0.2C charge for 1h30min, (11) Stage 11 rest for 15min, (12) Stage 12 0.5C discharge for 2h, (13) Stage 13 0.5C charge for 1h30min, (14) Stage 14 0.25C charge for 2h, (15) Stage 15 0.09C charge for 3h, wherein, vacuum is ended after the first hour, acid extraction is started after the second hour, and formation is ended after the acid extraction is completed.

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