CN115663175A - High-temperature container formation method for long-life valve-regulated lead-acid storage battery - Google Patents
High-temperature container formation method for long-life valve-regulated lead-acid storage battery Download PDFInfo
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- CN115663175A CN115663175A CN202211464630.5A CN202211464630A CN115663175A CN 115663175 A CN115663175 A CN 115663175A CN 202211464630 A CN202211464630 A CN 202211464630A CN 115663175 A CN115663175 A CN 115663175A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a high-temperature internal formation method of a long-life valve-controlled lead-acid storage battery, which is characterized in that a green plate is prepared by adopting a lead paste formula and adopting high-temperature high-humidity curing of positive lead paste, the positive active substance of an assembled battery contains two variants of alpha-PbO 2 and beta-PbO 2 in proper proportion after high-temperature formation, and the content of the two variants after formation determines the cycle life. Compared with a common container formation charging process, the high-temperature container formation charging method provided by the embodiment of the application has the advantage that the cycle life is greatly prolonged.
Description
Technical Field
The invention relates to the field of lead-acid storage batteries, in particular to a high-temperature container formation method of a long-life valve-controlled lead-acid storage battery, which is mainly applied to motorcycles.
Background
Formation refers to the process of electrochemically converting the material in the green plate into the charged active material, i.e. the positive plate is converted into PbO2 and the negative plate is converted into spongy metallic lead. The formation can make the polar plate generate a substance with higher activity, and the obtained active substance has a proper microstructure, so that the crystals have better contact, thereby ensuring that the polar plate has higher specific characteristics and long charge-discharge service life.
The valve-regulated lead-acid storage battery is also called VRLA storage battery, and the valve-regulated lead-acid storage battery has two formation modes: one is that the polar plate is formed and called and formed externally, the polar plate is formed into the electrode plate after charging in the forming trough, form and bring the electrode plate after the aftertreatment, inject the battery electrolyte of the stipulation requirement after the battery is assembled, get VRLA storage battery after charging according to the charging process; the other is battery formation commonly called container formation, namely, a battery is directly assembled by green plates, and charging formation is carried out after electrolyte is added, so that the VRLA battery is obtained.
Products after the anode is formed are alpha-PbO 2 and beta-PbO 2. The beta-PbO 2 ensures the performance, and the alpha-PbO 2 is used as a framework, so that the stable structure is ensured, and the service life of the storage battery is determined. alpha-PbO 2 is a complex crystal-like aggregate, and when the positive plate is formed in a low sulfuric acid concentration (even alkaline) and high temperature environment, the positive plate forms a part of alpha-PbO 2. The content of alpha-PbO 2 and beta-PbO 2 can determine the initial performance and the cycle life of the lead-acid storage battery, but for different types of storage batteries, the proper proportion is crucial, at present, most internal formation charging methods of domestic lead-acid storage battery manufacturers adopt medium-temperature formation, products after positive formation mainly use beta-PbO 2, and the cycle life of the storage batteries is poor in the using process. Therefore, how to solve the defects of the prior art is a subject of the present invention.
Disclosure of Invention
In order to solve the problems, the invention discloses a charging method for high-temperature container formation of a long-life valve-regulated lead-acid storage battery.
In order to achieve the above purpose, the invention provides the following technical scheme: lead plaster for a long-life valve-regulated lead-acid storage battery;
the lead paste comprises lead paste of a positive plate and lead paste of a negative plate;
the lead paste of the positive plate comprises the following components in parts by weight: 990-1010 parts of lead powder, 85-90 parts of dilute sulfuric acid, 110-115 parts of deionized water, 1-1.5 parts of short fibers, 0.8-1.2 parts of graphite and 0.6-1 part of 4BS0;
the lead plaster of the negative plate comprises the following components in parts by weight: 990-1010 parts of lead powder, 78-82 parts of dilute sulfuric acid, 115-120 parts of deionized water, 0.8-1 part of short fiber, 2.5-3 parts of humic acid and 7-9 parts of barium sulfide.
In the above aspect, the lead paste of the positive electrode plate further includes: 4-5 parts of red lead.
In the above aspect, the lead paste of the positive electrode plate further includes: 1.2-1.6 parts of antimony trioxide.
In the above scheme, the lead paste of the negative plate further comprises: 1.5-2 parts of acetylene black.
In the above aspect, the lead paste for the negative electrode plate further includes: 1-1.5 parts of lignin,
in the scheme, the following steps: comprises two stages of curing, wherein the curing temperature of the first stage is 73-77 ℃, and the humidity is 99%;
the curing temperature of the second stage is 68 +/-2 ℃, and the humidity is 97%.
In the above scheme, the curing time of the first stage is 5h, and the curing time of the second stage is 9h.
The beneficial effects of the invention are as follows: the green plate is prepared by adopting the lead plaster formula and the anode lead plaster through high-temperature high-humidity curing, the anode active substance contains two variants of alpha-PbO 2 and beta-PbO 2 with proper proportion after the assembled battery is formed at high temperature, and the cycle life is determined by the content of the two variants after the assembled battery is formed. Compared with a common internal formation charging process, the high-temperature internal formation charging method provided by the embodiment of the application has the advantage that the cycle life is greatly prolonged.
Detailed Description
In the embodiment of the application, a charging method for high-temperature internal formation of a long-life valve-regulated lead-acid storage battery is provided, so that the service life of the valve-regulated lead-acid storage battery for a motorcycle can be prolonged.
The embodiment of the application comprises formation dilute sulfuric acid density, charging current, formation time and temperature control. After the assembly process of the storage battery is finished, a certain amount of dilute sulfuric acid is injected, and the density of the dilute sulfuric acid is 1.225g/cm 3 And +/-0.001 (25 ℃), and after the small holes of the diaphragm, the small holes of the positive plate active matter and the negative plate active matter and the dilute sulfuric acid are fully soaked, the direct-current battery is connected for charging. 1.225g/cm 3 Cooling the diluted sulfuric acid of +/-0.001 (25 ℃) before injecting the diluted sulfuric acid into the storage battery finished by the assembly process, wherein the diluted sulfuric acid is cooled toAnd (3) at 10 ℃, putting the storage battery into cooling water after liquid injection, controlling the internal temperature of the battery to be 45 +/-5 ℃, and standing the storage battery in the water for 0.5h after the storage battery is injected with 10 ℃ dilute sulfuric acid to start charging. The formation of the VRLA storage battery adopts a multi-section constant-current charging formation process, the formation current is the most main process parameter of the formation process, the formation current is too small, the formation reaction is slow, and a large amount of PbSO is produced 4 Difficult to be formed; when the current is too large, the side reaction of water decomposition increases, the charging efficiency is lowered, and the electrode plate is likely to generate powder removal or air bubbles, so that it is important to select an appropriate charging current. The formation time of the VRLA storage battery for the motorcycle is adjusted according to the thickness of a plate, and the key points of the process are mainly the determination of charging current and time, and the time to which the charging is carried out, the discharging depth and the like, and when the charging is close to complete charging, the discharging is reasonable. The temperature is a weight parameter of formation, the control of the formation temperature is an important condition for ensuring that the polar plate has reasonable crystals and optimal components, and the ideal formation temperature is 58-64 ℃.
The long-life valve-regulated lead-acid storage battery lead paste comprises a positive plate lead paste and a negative plate lead paste, wherein the positive plate lead paste comprises the following components in parts by weight: 990-1010 parts of lead powder, 85-90 parts of dilute sulfuric acid, 110-115 parts of deionized water, 1-1.5 parts of short fibers, 0.8-1.2 parts of graphite, 0.6-1 part of 4BS0.6, 4-5 parts of red lead and 1.2-1.6 parts of antimony trioxide; the lead plaster of the negative plate comprises the following components in parts by weight: 990-1010 parts of lead powder, 78-82 parts of dilute sulfuric acid, 115-120 parts of deionized water, 0.8-1 part of short fiber, 2.5-3 parts of humic acid, 1-1.5 parts of lignin, 7-9 parts of barium sulfide and 1.5-2 parts of acetylene black.
The positive lead paste is cured by adopting a high-temperature high-humidity process and is cured in two stages, wherein the curing temperature of the first stage is 75 +/-2 ℃, the humidity of the first stage is 99 percent, the curing time is 5 hours, the curing temperature of the second stage is 68 +/-2 ℃, the humidity of the second stage is 97 percent, and the curing time is 9 hours, so that 4PbO & PbSO can be obtained 4 A green plate as a main component. The negative lead plaster is cured by adopting a medium-temperature high-humidity process, wherein the curing temperature is 45 +/-5 ℃, the humidity is 99 percent, and the curing time is 48 hours. When the storage battery is formed in the container at 58-64 ℃, 3BS, 4BS and PbO in the positive green plate are combined with water, so that the PH of the solution in the hole is increasedThe value is increased, electrochemical reaction is carried out in the inner area of the polar plate, and alpha-PbO with proper proportion is formed 2 The cycle life of the storage battery is prolonged.
According to the high-temperature internal formation charging method, the lead paste formula and the positive lead paste are adopted to prepare the green plate through high-temperature high-humidity curing, and the positive active substance of the assembled battery contains alpha-PbO in a proper proportion after high-temperature formation 2 And beta-PbO 2 Two variants, the content of the latter two variants determining the cycle life. Compared with a common internal formation charging process, the high-temperature internal formation charging method provided by the embodiment of the application has the advantage that the cycle life is prolonged by more than 50%.
Attached table 1. High temperature internal formation charging method of embodiment
(BTX 14-BS (MF) is exemplified by 12V12Ah, C is the 10h rate capacity value of the battery)
Attached table 2 conventional control container formation charging method
(BTX 14-BS (MF) is an example, 12V12Ah, C is a 10h rate capacity value of the battery)
The content of lead dioxide is detected by an X-ray diffractometer (XRD), and the detection results are shown in the attached table 3.
FIG. 3 is a table showing the relationship between formation conditions and parameters of positive electrode active material
The batteries obtained in the above examples and comparative examples had heavy load lives as shown in Table 4
Method for testing service life, standard conditions:
assembling the green plate prepared by the lead plaster formula and the curing method according to a BTX14-BS (MF) assembly process, filling acid, performing high-temperature internalization charging to obtain the lead-acid storage battery, and performing performance test.
1) Heavy load life test:
lead-acid storage batteries for motorcycles in accordance with Japanese Industrial Standard JISD5302: 2004;
2) Discharging at 40-45 deg.c for 1 hr in constant current 5A and charging at 1.25A for 5 hr, with the charging and discharging cycle being 1 time life; continuously discharging at 5A current every 25 times, and stopping the voltage at 10.2V; when the discharge capacity was less than 40% of the rated capacity, it was confirmed that the rise was no longer the end of the test;
3) The heavy load service life is required to be more than or equal to 250 times.
Attached table 4 comparison of the heavy load life of the storage battery
| Serial number | Number of times of life | Standard requirements | Comparative example C 10 ％ | Example C 10 ％ |
| 1 | 25 | ≥40％ | 110.6％ | 108.2 |
| 2 | 50 | ≥40％ | 99.5 | 105.4 |
| 3 | 75 | ≥40％ | 90.7 | 101.2 |
| 4 | 100 | ≥40％ | 81.2 | 95.3 |
| 5 | 125 | ≥40％ | 72.6 | 91.7 |
| 6 | 150 | ≥40％ | 63.4 | 87.2 |
| 7 | 175 | ≥40％ | 52.9 | 83.4 |
| 8 | 200 | ≥40％ | 41.6 | 80.1 |
| 9 | 225 | ≥40％ | 35.8 (end of Life) | 76.8 |
| 10 | 250 | ≥40％ | 72.6 | |
| 11 | 275 | ≥40％ | 68.7 | |
| 12 | 300 | ≥40％ | 65.2 | |
| 13 | 325 | ≥40％ | 61.3 | |
| 14 | 350 | ≥40％ | 56.5 | |
| 15 | 375 | ≥40％ | 51.9 | |
| 16 | 400 | ≥40％ | 45.8 | |
| 17 | 425 | ≥40％ | 38.7 (end of Life) |
It should be noted that the above-mentioned contents only illustrate the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and it is obvious to those skilled in the art that several modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations fall within the protection scope of the claims of the present invention.
Claims (6)
1. The utility model provides a high life valve regulated lead acid battery diachylon which characterized in that:
the lead paste comprises lead paste of a positive plate and lead paste of a negative plate;
the lead paste of the positive plate comprises the following components in parts by weight: 990-1010 parts of lead powder, 85-90 parts of dilute sulfuric acid, 110-115 parts of deionized water, 1-1.5 parts of short fibers, 0.8-1.2 parts of graphite and 0.6-1 part of 4 BS;
the lead plaster of the negative plate comprises the following components in parts by weight: 990-1010 parts of lead powder, 78-82 parts of dilute sulfuric acid, 115-120 parts of deionized water, 0.8-1 part of short fiber, 2.5-3 parts of humic acid and 7-9 parts of barium sulfide.
2. The high life valve-regulated lead-acid battery lead paste of claim 1, wherein: the lead paste of the positive plate further comprises: 4-5 parts of red lead.
3. The high life valve-regulated lead-acid battery lead paste of claim 2, wherein: the lead paste of the positive plate further comprises: 1.2-1.6 parts of antimony trioxide.
4. The high life valve-regulated lead-acid battery lead paste of claim 3, wherein: the lead paste of the negative plate further includes: 1.5-2 parts of acetylene black.
5. The high life valve-regulated lead-acid battery lead paste of claim 4, wherein: the lead paste of the negative plate further comprises: 1-1.5 parts of lignin,
the method for curing the lead plaster of the high-life valve-regulated lead-acid storage battery according to claim 1, which is characterized in that: comprises two stages of curing, wherein the curing temperature of the first stage is 73-77 ℃, and the humidity is 99 percent;
the curing temperature of the second stage is 68 +/-2 ℃, and the humidity is 97%.
6. The method for curing the lead plaster of the high-life valve-regulated lead-acid battery according to claim 6, characterized in that: the curing time of the first stage is 5h, and the curing time of the second stage is 9h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211464630.5A CN115663175A (en) | 2022-11-22 | 2022-11-22 | High-temperature container formation method for long-life valve-regulated lead-acid storage battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211464630.5A CN115663175A (en) | 2022-11-22 | 2022-11-22 | High-temperature container formation method for long-life valve-regulated lead-acid storage battery |
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| CN202211464630.5A Pending CN115663175A (en) | 2022-11-22 | 2022-11-22 | High-temperature container formation method for long-life valve-regulated lead-acid storage battery |
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