CN116008825B - High-temperature life pre-judging method for valve-regulated lead-acid storage battery - Google Patents
High-temperature life pre-judging method for valve-regulated lead-acid storage battery Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000003860 storage Methods 0.000 title claims abstract description 34
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 30
- 238000012360 testing method Methods 0.000 claims abstract description 87
- 238000010521 absorption reaction Methods 0.000 claims abstract description 10
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- 230000004580 weight loss Effects 0.000 claims description 7
- 230000020477 pH reduction Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000011161 development Methods 0.000 abstract description 5
- 238000013100 final test Methods 0.000 abstract description 4
- 208000028659 discharge Diseases 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000013480 data collection Methods 0.000 description 2
- 239000011505 plaster Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000003797 telogen phase Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A high-temperature life pre-judging method for a valve-regulated lead-acid storage battery mainly comprises the following steps: (1) recording the weight of the valve-regulated lead-acid storage battery before acid addition and the weight after formation, and calculating the effective acid quantity m of the battery 1 The method comprises the steps of carrying out a first treatment on the surface of the (2) Measuring and recording saturated acid absorption amount m of valve-regulated lead-acid storage battery 2 The method comprises the steps of carrying out a first treatment on the surface of the (3) Calculating the saturation s' before SAEJ2801 test after the formation of the valve-regulated lead-acid storage battery; (4) the battery is subjected to a high-temperature life SAEJ2801 test, and the weight of the battery after each unit of test is recorded in the test process; (5) calculating the water loss of each unit of test and the saturation of the battery after each unit of test; (6) the high temperature lifetime SAEJ2801 unit number prediction is performed according to the data. Estimated SAEJ2801 lifetime unit number= (s '-s')/(m) e ÷m 2 ) +K, where s' is the critical saturation and K is the delay factor. The method can accurately estimate the final test result of the SAEJ2801 service life 4-12 weeks in advance, and greatly improve the test efficiency or project development progress.
Description
Technical Field
The invention belongs to the technical field of lead-acid storage batteries, and particularly relates to a high-temperature service life pre-judging method of a valve-controlled lead-acid storage battery.
Background
The high-temperature life test of the current valve-regulated lead-acid storage battery mainly comprises an SAE J2801 test (75 ℃), an SAE J240 test (75 ℃), a 60 ℃ water loss test and the like.
Wherein SAEJ2801 service life is one of the most important high temperature performances of a lead-acid storage battery, and the main failure modes of the service life test of the valve-regulated lead-acid storage battery SAEJ2801 are as follows: and the positive grid corrodes and creep grows up. Anatomical data display: after the service life of the SAEJ2801 is tested, the positive grid is severely corroded and grown, and the positive grid contacts the negative bus bar upwards and pierces the separator downwards; the grid ribs are corroded and broken, and the positive lead plaster is separated from the positive grid; the water loss of the polar group is serious, and the lead plaster is dry.
SAEJ2801 test procedure is as follows:
1. battery full charge treatment
2. The test is carried out in a water bath tank with the temperature of 75.0 (+ -3.0) DEG C, and the liquid level of the water bath is more than or equal to 75 percent of the total height of the battery tank.
3. The test cycle was performed as described below:
25a is discharged for 18 seconds,
b.14.2V charging for 30 min, current limit 25A
3A was discharged for 15 minutes,
d.14.2V charging for 30 min, current limit 25A
e.25a is discharged for 18 seconds,
f.14.2V charge for 30 min, current limit 25A
g.3A discharge for 15 min
h.14.2V charge for 30 min, current limit 25A
i.3A discharge for 15 min
j.14.2V charge for 29 min 24 sec, current limit 25A
The cycle was continued according to steps a-j for a total of 6 cycles. Each cycle took 3.25 hours and each cycle was shared 6 times for 19.5 hours.
k. After the 6 th cycle, discharge at 10A for 15 minutes, charge at 14.2V current limit 25A for 255 minutes (4 hours 15 minutes) for a total of 24 hours
Repeating steps a-k for 5 days (24 hours for 1 completion of steps a-k, 5 times for 24 hours, i.e. 5 days)
Repeating the steps a-j for 4 times
n.10A discharge for 15 minutes
o. charging with 14.2V current limit 25A for 120 minutes (2 hours)
The test described in step 3 was run for a total of 34 cycles (one cycle being defined as a-j in step 3) for a total of one week, step 3 was successfully tested.
In the above test procedure, the transition delay from the end of charge to the start of discharge and from the end of discharge to the start of charge cannot exceed 10 seconds.
4. The battery assembly is opened and kept stand for 28-33 hours in a water bath at 75+/-3 ℃ and the open-circuit voltage is measured to judge whether the test termination condition is reached.
5. The cell was kept in the water bath in step 4 and discharged at 200A to 7.2V for at least 10 seconds.
6. The above test steps 3 to 5 are repeated without recharging (the complete test steps 3 to 5 are 1 unit).
The life test is terminated (as long as the termination condition is not reached, test from step 3 to step 5; until the termination condition is triggered, test termination) if any of the following occurs:
at the end of any 30-minute charging step, the battery has a charging current greater than 15A
-at any discharge stage, the cell voltage is below 7.2V
At the end of the rest phase, the cell terminal voltage falls below 12.0V
And when the battery fails, counting the number of the cyclic test units.
According to the SAEJ2801 test program, the high-temperature life test steps are complex, the life test period is long, and particularly for a valve-regulated lead-acid storage battery, the SAEJ2801 life test period is generally not less than 4 months, so that the high-temperature life performance of the detected battery is not convenient to evaluate quickly, and the timely improvement optimization of research work or the rapid promotion of project development is not facilitated.
Disclosure of Invention
In order to overcome the defects in the background art, the invention aims to provide the high-temperature life predicting method for the valve-regulated lead-acid storage battery, which can accurately predict the final test result of the service life of the SAEJ2801 4-12 weeks in advance and greatly improve the test efficiency or the project development progress.
The technical scheme of the invention comprises the following steps:
the method comprises the following steps:
(1) recording the weight of the valve-regulated lead-acid storage battery before acid addition and the weight after formation, and calculating the effective acid amount m of the battery 1 =weight after end of battery formation-weight before battery acidification;
(2) measuring and recording saturated acid absorption amount m of valve-regulated lead-acid storage battery 2 The method comprises the steps of carrying out a first treatment on the surface of the The same batch of batteries are produced, the same materials and the same process are used, and the same group of saturated acid absorption data can be used;
(3) calculating the saturation degree before SAEJ2801 test after formation of the valve-regulated lead-acid storage battery, wherein the saturation degree s' =effective acid amount/saturated acid absorption amount;
(4) the battery is subjected to a high-temperature life SAEJ2801 test, and the weight of the SAEJ2801 before the start of the test and after each unit of test is recorded in the test process;
(5) calculating weight loss of each unit test and saturation of the battery after each unit test;
(6) and (3) carrying out high-temperature service life SAEJ2801 unit number prejudgment according to the data:
when the number of SAEJ2801 test units is not less than 4 and the saturation s of the current test unit is not lower than the critical saturation s', the number of SAEJ2801 final life units of the valve-controlled battery can be pre-judged, and the average weight loss m per unit of the current test unit is calculated e Estimated SAEJ2801 lifetime unit number= (s' -s ")/(m e ÷m 2 ) +K, where K is the delay factor.
The critical saturation s' is 87+/-2 percent.
The critical saturation s 'is 87% -89%, which is mainly influenced by the characteristics of the separator, and the better the wet permeability of the separator is, the higher the critical saturation s'.
The delay coefficient K is 1-3, and is mainly influenced by the corrosion resistance and creep resistance of the positive grid, and the stronger the corrosion resistance and creep resistance of the positive grid, the larger the K value.
The cells were subjected to performance testing prior to SAEJ2801 testing, including C20 capacity testing, -18 ℃ low temperature testing.
The C20 capacity test is 1-4 times, and the low temperature test at-18 ℃ is 1-4 times.
The C20 capacity test is 2 times or 3 times, and the-18 ℃ low-temperature test is 2 times or 3 times.
The invention is based on the saturation data of the valve-regulated lead-acid storage battery and the process data of SAEJ2801 life test, and can calculate, analyze and pre-judge, so that the final test result of the SAEJ2801 life can be estimated more accurately 4-12 weeks in advance, and the test efficiency or the project development progress can be greatly improved.
The existing valve-regulated lead-acid storage battery high-temperature life test steps are complex, the life test period is long, and how to quickly evaluate the high-temperature life performance of the detected battery is a problem which is difficult to solve. The inventor finds through analysis and research that an important sign of the service life of the SAEJ2801 of the valve-regulated lead-acid storage battery is that the saturation of the electrolyte is reduced to a critical value (about 87+/-2%), after the saturation of the electrolyte is reduced to the critical value, a gas channel in a separator is very smooth, and oxygen precipitated from the positive electrode is very easy to diffuse to the negative electrode to undergo a reduction reaction (oxygen circulation reaction), and meanwhile, the reaction emits heat. The oxygen cycling reaction causes the anode potential to move forward, which correspondingly causes the anode potential to move forward, the oxygen evolution current of the anode to increase, the water loss of the battery to further reduce the saturation of the electrolyte, and the internal resistance of the battery to increase, so that a aggravated cycle (i.e. thermal runaway) is formed.
The invention has the beneficial effects that: the invention is based on the saturation data of the valve-regulated lead-acid storage battery and the process data of SAEJ2801 life test, and can accurately predict the final test unit number of the high-temperature life SAEJ2801 of the valve-regulated lead-acid storage battery 4-12 weeks in advance, thereby being convenient for timely adjusting the scheme or optimizing and improving, and greatly improving the test efficiency or the project development progress.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by persons skilled in the art without making creative efforts based on the embodiments of the present invention are all within the protection scope of the present invention.
Examples
Taking a 60AhAGM start-stop cell as an example:
(1) weigh and record the weight m of the battery before acid addition 0 13.871kg (sample 1) and 13.741kg (sample 2), respectively, and 17.644kg (sample 1) and 17.490kg (sample 2) of the battery formation end (without a safety valve) were weighed and recorded, and the effective acid amount m of sample 1 was calculated 1 17.644kg-13.871 kg= 3.773kg, sample 2 effective acid amount m 1 ＝17.490kg-13.741kg＝3.749kg。
Sample 1 and sample 2 are the same batch of cells produced using the same materials and the same process.
(2) Selecting cells produced in the same batch as sample 1 and sample 2 (same process using the same materials), measuring and recording saturated acid absorption m of the cells 2 = 3.984kg. The saturated acid absorption amount measuring method is shown in China patent for details, namely an AGM storage battery acid amount saturation testing method, and the method has the following issued bulletin number: CN109612868B, authorized bulletin day: 20221225.
(3) calculating the saturation of the formed valve-regulated lead-acid storage battery, wherein the saturation s' =effective acid amount/saturated acid absorption amount of the formed storage battery.
Sample 1 saturation s' = 3.773/3.984 x 100% =94.7%;
sample 2 saturation s' = 3.749/3.984 x 100% =94.1%.
(4) After the effective acid amount s' is measured by the test battery, a safety valve (or referred to as an exhaust plug) is arranged to prepare a finished battery, and the weights of the safety valves of the battery 1 and the battery 2 are 36g (0.036 kg). The finished battery was tested for performance within 2 weeks after production offline, and was tested for C20 capacity twice and low temperature twice at-18 ℃ prior to SAEJ2801 testing.
Sample 1 and sample 2 batteries were subjected to high temperature life SAEJ2801 testPre-weighing and recording weight m 3 17.643kg and 17.488kg, respectively, and the weight m after each unit of test (i.e. after each step 5 of the SAEJ2801 test procedure) was recorded during the SAEJ2801 test 4 See tables 1 and 2 for details.
(5) The weight loss per unit test and the saturation of the battery after each unit test were calculated and are detailed in tables 1 and 2.
The saturation calculation mode of the battery after each unit test is as follows: (SAEJ 2801 weight per unit test-safety valve weight-weight before battery formation acid addition)/saturated acid absorption 100%, i.e. saturation of battery per unit test= (m) 4 -0.036-m 0 )/m 2 *100％
For example, sample 1 cell saturation calculation for 1 st cell: (17.618-0.036-13.871)/3.984 x 100% = 93.1%, saturation calculation of sample 1 cell 2 nd cell: (17.600-0.036-13.871)/3.984 x 100% = 92.7%, and so on.
The critical saturation s' of the test battery takes 87 percent, and when the number of the test units of the SAEJ2801 is equal to or larger than 4 and the saturation is not lower than 87 percent, the SAEJ2801 can be estimated.
(6) For sample 1 battery, taking the first 4 units of test data for pre-judgment:
average weight loss per unit m e ＝(0.025+0.018+0.018+0.018)/4＝0.020kg；
SAEJ2801 lifetime unit number= (s' -s ")/(m e ÷m 2 ) +K, where K has a value of 2
SAEJ2801 lifetime unit number= (94.7% -87%)/(0.020 +. 3.984) +2=15.34+2+.17)
Sample 1 battery measured SAEJ2801 life was 16 units (17 units discharged 10s voltage below 7.2V, test terminated), very close to the life units predicted from the previous 4 unit test data.
Table 1 battery sample 1SAEJ2801 test data collection
For sample 2 cells, pre-judgment was performed with the first 4 units of test data:
average weight loss per unit m e ＝(0.025+0.020+0.016+0.023)/4＝0.021kg；
SAEJ2801 lifetime unit number= (s' -s ")/(m e ÷m 2 ) +K, where K has a value of 2
SAEJ2801 lifetime unit number= (94.1% -87%)/(0.021 ≡ 3.984) +2=13.47+2+.15 ≡
The life of the sample 2 battery measured SAEJ2801 is 15 units (16 units are not discharged and the test is terminated), and the number of life units is consistent with that of the previous 4 units of test data.
Table 2 battery sample 2SAEJ2801 test data collection
The above describes in detail a method for predicting the high-temperature life of a valve-regulated lead-acid battery provided by the embodiment of the present invention, and specific examples are applied to illustrate the principle and implementation of the present invention, and the above description of the embodiment is only used to help understand the method and core idea of the present invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (7)
1. A high-temperature service life pre-judging method for a valve-regulated lead-acid storage battery is characterized by comprising the following steps of: the method comprises the following steps:
(1) recording the weight of the valve-regulated lead-acid storage battery before acid addition and the weight after formation, and calculating the effective acid amount m of the battery 1 =weight after end of battery formation-weight before battery acidification;
(2) measuring and recording saturated acid absorption amount m of valve-regulated lead-acid storage battery 2 ；
(3) Calculating the saturation degree before SAEJ2801 test after formation of the valve-regulated lead-acid storage battery, wherein the saturation degree s' =effective acid amount/saturated acid absorption amount;
(4) the battery is subjected to a high-temperature life SAEJ2801 test, and the weight of the SAEJ2801 before the start of the test and after each unit of test is recorded in the test process;
(5) calculating weight loss of each unit test and saturation of the battery after each unit test;
(6) and (3) carrying out high-temperature service life SAEJ2801 unit number prejudgment according to the data:
when the number of SAEJ2801 test units is equal to or greater than 4 and the saturation s of the current test unit is not lower than the critical saturation s', the number of SAEJ2801 final life units of the valve-controlled battery can be pre-judged, and the average weight loss m per unit of the current test unit is calculated e Estimated SAEJ2801 lifetime unit number= (s '-s')/(m) e ÷m 2 ) +K, where K is the delay factor.
2. The method for predicting the high-temperature life of the valve-regulated lead-acid storage battery according to claim 1, wherein the method comprises the following steps of: the critical saturation s″ is in the range of 87.+ -. 2%.
3. The method for predicting the high-temperature life of the valve-regulated lead-acid storage battery according to claim 1, wherein the method comprises the following steps of: the critical saturation s' is 87% -89%.
4. The method for predicting the high-temperature life of the valve-regulated lead-acid storage battery according to claim 1, wherein the method comprises the following steps of: the delay factor K is 1-3.
5. The method for predicting the high-temperature life of the valve-regulated lead-acid storage battery according to claim 1, wherein the method comprises the following steps of: the cells were subjected to performance testing prior to SAEJ2801 testing, including C20 capacity testing, -18 ℃ low temperature testing.
6. The method for predicting the high-temperature life of the valve-regulated lead-acid storage battery according to claim 5, wherein the method comprises the following steps of: the C20 capacity test is 1-4 times, and the low temperature test at-18 ℃ is 1-4 times.
7. The method for predicting the high-temperature life of the valve-regulated lead-acid storage battery according to claim 5, wherein the method comprises the following steps of: the C20 capacity test is 2 times or 3 times, and the-18 ℃ low-temperature test is 2 times or 3 times.
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