CN104459561B - Method for measuring lead dendrite crystal short-circuiting of superfine glass fiber partition boards of lead-acid storage battery - Google Patents

Method for measuring lead dendrite crystal short-circuiting of superfine glass fiber partition boards of lead-acid storage battery Download PDF

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Publication number
CN104459561B
CN104459561B CN201510001788.2A CN201510001788A CN104459561B CN 104459561 B CN104459561 B CN 104459561B CN 201510001788 A CN201510001788 A CN 201510001788A CN 104459561 B CN104459561 B CN 104459561B
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lead
superfine glass
battery
short
glass fibre
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CN104459561A (en
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郭永榔
曾燕真
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Fuzhou University
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Fuzhou University
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Abstract

The invention discloses a method for measuring lead dendrite crystal short-circuiting of superfine glass fiber partition boards of a lead-acid storage battery. The method includes the following steps that (1), the superfine glass fiber partition boards and pure lead sheets to be measured are cut and used for preparing a testing battery; (2), constant-current charging is performed on the testing battery, a voltage-time curvature is measured and drawn, and therefore a time value from initial charging to short-circuiting is obtained; (3), voltage changes of the testing battery in the process of constant-current charging are determined, and whether short-circuiting easily occurs on the superfine glass fiber partition boards is judged through the measured numerical values. Through designing a device for simulating the formation charging condition of the battery, whether short-circuiting easily occurs on the AGM partition boards inside the battery in the formation charging process or not is judged, so that the suitable AGM partition board used for the valve regulation type lead-acid storage battery is rapidly judged and selected. The method is easy to implement, the experimental instrument is simple and easy to obtain, the detection cycle is obviously shortened, and the method is worthy of popularization.

Description

The method of measurement lead-acid accumulator superfine glass fibre partition board lead dendritic crystal short circuit
Technical field
The invention belongs to the detection field of battery separator short circuit, and in particular to a kind of measurement lead-acid accumulator superfine glass is fine The method of dimension dividing plate lead dendritic crystal short circuit.
Background technology
Lead-acid accumulator both positive and negative polarity life plate is mainly by lead oxide (PbO), basic lead sulphate (3PbOPbSO4·H2O or 4PbO·PbSO4), lead sulfate (PbSO4) and a small amount of free lead composition, production process makes positive and negative electrode turn respectively by formation charging Turn to Lead oxide brown (PbO2) and metal sponge lead (Pb) active substance, being melted at present mainly has tank formation and is internalized into two kinds of sides Method.Be powered chemical conversion before, pole plate needs the pickling process for first carrying out 1-2 hours, make lead oxide be converted into basic lead sulphate and Lead sulfate, while water is generated, and the different parts in pole group produce H2SO4Gradient and the big calorimetric of releasing.Due to VRLA , using structure is closely assembled, hot specific volume is low for accumulator, and the heat that reaction is produced can not be dispersed again in time, internal temperature of battery is drastically gone up Rise, highest can be more than 65 DEG C.Battery temperature is raised and H2SO4The generation of gradient so that the lead sulfate that polar board surface is formed is in temperature The position dissolubility that degree is high and sulfuric acid concentration is low becomes big, and this greatly increased the wind that battery charging process occurs dendrite short circuit Danger.
Ultra-fine fibre glass (AGM) dividing plate that analysing valve control type lead-acid accumulator battery is adopted contains the tiny micropore of two kinds of structures, and one Kind it is parallel to the micropore of septum plane, another kind is perpendicular to the relatively large micropore of septum plane, the latter is conducive to oxygen to negative Pole is spread, but is also the path of dendritic lead growth, as in dividing plate, more lead sulfates are easily deposited on raw glass fiber, When this causes to charge, dendrite lead is grown readily along crude fibre, so as to cause micro-short circuit between pole plate.
The method for reducing dendrite short circuit in prior art mainly has：(1) before sulfuric acid electrolyte is added to battery, will Sulfuric acid electrolyte is cooled to less than 0 DEG C, takes necessary cooling measure after battery acid adding again, and such as water-cooled, air cooling etc. is controlling to fill The intensification of electric process inside battery；(2) add a certain amount of sulphate additives in the electrolytic solution, utilize " common-ion effect " To suppress PbSO4Dissolubility；(3) accelerate sulphuric acid enter inside battery, it is to avoid local sulfuric acid concentration it is too low and increase PbSO4It is molten Xie Du, such as adopts vacuum acid feeding method.In addition to above-mentioned three kinds of methods, additive is also generally adopted, to improve lead-acid accumulator Can, additive is strong electrolyte.
At present the detection method of dendrite short circuit is mainly by the loop test to battery or according to national standard The method recharged after carrying out short-circuit overdischarge in 21 days is tested.The time cycle that the method needs is long, and needs substantial amounts of Battery.It is anxious to be resolved at present and tackling key problem technical barrier that whether quick detection dividing plate easily produces dendrite lead short circuit.
The content of the invention
Present invention aims to the deficiencies in the prior art, there is provided a kind of measurement lead-acid accumulator ultra-fine fibre glass The method of dividing plate lead dendritic crystal short circuit.The method operating process is simple, and experimental apparatus are simple and easy to get, hence it is evident that shorten detection cycle, It is worthy to be popularized.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of method of measurement lead-acid accumulator superfine glass fibre partition board lead dendritic crystal short circuit, comprises the following steps：
（1）Using 2 pure lead flakes as positive and negative pole plate, superfine glass fibre partition board to be measured is put between 2 lead flakes, group Dress test cell apparatus；
（2）Constant-current charge is carried out to testing battery, survey and draw voltage-time curve, obtain Time value；It is to judge whether AGM dividing plates are susceptible to the key parameter of short circuit from the time value that is short-circuited is started to charge up to.
（3）Determine test change in voltage of the cell apparatus in constant-current charge.
Step（1）Specially：
1. the pure lead flake 2 for selecting surface smooth, as the positive and negative pole plate of test battery；
2. copper conductor is welded on into positive and negative electrode top of the plate portion lug position, and the position welded with epoxy sealing well, is made For power cord connector；
3. cutting superfine glass fibre partition board to be measured so as to which size is more bigger than positive and negative electrode board size；
4. 10-60 s in the lead-acid accumulator green plate immersion 30-40 wt% sulfuric acid solutions of 4 solidifications are taken, pole plate table is made Face generates lead sulfate, is positioned over 5-10 min in air, the sulphuric acid of polar board surface is fully reacted after taking-up；
5. rectangle cell body is obtained with poly (methyl methacrylate) plate, and 4 green plates after step 4. pickling is put in groove, and plus Enter deionized water, submergence pole plate, 2 h of constant temperature at 50 DEG C take out whole pole plates, be left solution；
6. superfine glass fibre partition board to be measured is immersed and take out after step solution 5., be placed between 2 pure lead flakes, by lead After piece-superfine glass fibre partition board-lead flake to be measured is stacked successively, it is put in transparent plastic bag, on the both sides of transparent plastic bag Poly (methyl methacrylate) plate in fixation, adds a pressure transducer between poly (methyl methacrylate) plate and plastic bag, and whole device is applied to press Power；
7. toward plastic bag, add the sulfuric acid solution of 2-10wt%, the amount of solution to be defined by the lug for not having pole plate, assemble To test cell apparatus.
Step（2）Specially：
Test battery is placed in 50 DEG C of temperature chambers, constant-current charge is carried out, the voltage-time curve of battery is surveyed and drawn, is worked as electricity When pressure declines suddenly, show on superfine glass fibre partition board, to there occurs short circuit, record from starting to charge up to time for being short-circuited Value, the value are for judging whether AGM dividing plates are susceptible to the key parameter of short circuit.
Step（3）Specially：During constant-current charge, the magnitude of voltage of test battery is determined；Described constant-current charge electricity Flow valuve is the product of the apparent current density with the area of test battery pole plates of battery pole plates in Battery formation charging process.
The beneficial effects of the present invention is：
1）Formation charging condition of the present invention by simulated battery, can judge whether AGM dividing plates charge in container formation Process is easily caused short circuit, so as to quickly judge and pick out suitable analysing valve control type lead-acid accumulator battery AGM dividing plates；
2）Dendrite lead forming process in the battery is complicated and is difficult to observe, and is well understood to dendrite lead by the method and exists The process formed in battery, provides good theoretical foundation to find the short circuit of dendrite inhibition lead；
3）Compared to short-circuit overdischarge in 21 days of national standard and then the detection method for recharging, the method operating process letter Single, experimental apparatus are simple and easy to get, hence it is evident that shorten detection cycle；
4）General measure analysing valve control type lead-acid accumulator battery glass fibre（AGM）The method of dividing plate lead dendritic crystal short circuit needs to consume big Amount battery, and the present invention replaces battery with pure stereotype, so as to save experiment material cost；
5）The present invention is applied to the detection of various valve-control storage battery glass fibre separators, can be used as judgement dividing plate performance quality And improve analysing valve control type lead-acid accumulator battery performance and prolong long-life important method.
Description of the drawings
Fig. 1 be test cell apparatus schematic diagram, 1 copper cash, 2 dividing plates, 3 pure Pb plates, 4 screws, 5 transparent plastic bags, 6 have Machine glass plate, 7 pressure transducers, 8 nuts；
Fig. 2 is the voltage-vs-time at the simulation test constant-current charging of battery process positive/negative plate two ends of different AGM block board thicknesses Curve；
In Fig. 3：(a) simulation test battery be short-circuited after AGM dividing plate photos, (b) AGM dividing plates location of short circuit Enlarged photograph, (c) SEM photograph of AGM dividing plates location of short circuit.
Specific embodiment
The present invention further illustrates the present invention with the following example, but protection scope of the present invention is not limited to following reality Apply example.
Embodiment 1
Measure the side of AGM block board thicknesses that 12 V, 12 Ah analysing valve control type lead-acid accumulator batteries use to dendrite lead Effect of Short Circuit Method：
Test cell apparatus：The green plate of 4 solidifications immerses 1.255 g/cm310 s in sulfuric acid solution, taking-up shelve 5 Min, is put into internal diameter size for 9 × 4.5 × 1.5 cm3Lucite groove in, add 30 mL deionized waters, 50 DEG C 2 of constant temperature H, takes out whole pole plates；It is put in organic glass guide channel with AGM dividing plates after soaking and polar plate area size is 20 cm2 ( 4×5 Cm the smooth pure Pb pieces of two panels plane) are assembled into simulated battery, are put in plastic bag, add 2wt% sulfuric acid solutions, amount of solution It is defined by the lug for not having pole plate；Then apply 80 kPa of pressure to simulated battery two ends, test battery is placed in into 50 DEG C of constant temperature In groove, and with 40 mA electric current trickle charges.
Fig. 2 is the voltage-vs-time at the simulation test constant-current charging of battery process positive/negative plate two ends of different AGM block board thicknesses Curve.When voltage declines suddenly, show short circuit to be there occurs on AGM dividing plates, use from time value T that is short-circuited is started to charge up to Whether the key parameter of short circuit is susceptible in judgement AGM dividing plates.To different AGM dividing plates, its ultra-fine fibre glass thickness is different, Porosity is different, and characteristic is also different, and time value T that is so short-circuited is also just different.
Internal structure after AGM dividing plates are short-circuited is as shown in Figure 3.(a) be test battery be short-circuited after AGM every Plate photo, (b) be AGM dividing plate location of short circuit enlarged photograph, (c) SEM photograph of AGM dividing plates location of short circuit.On AGM dividing plates There is the speckle of some black after short circuit, these are dendrite lead.When the dendrite lead for being formed is more, the secondary structure between dendrite It is connected with each other, forms needle prick shape flowering shrubs structure, shown in such as Fig. 3 (b)；From the SEM photograph of Fig. 3 (c) it can be seen that dendrite to While front growth, the secondary structure of side also little by little grows, and the branch of each dendrite first grows up to acicular texture.Dendrite Shape lead is little by little grown by one lateral positive pole of negative pole, the penetrating clapboard when growing to a certain extent, causes the short circuit of battery.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with Modification, should all belong to the covering scope of the present invention.

Claims (6)

  1. It is 1. a kind of to measure the short-circuit method of lead-acid accumulator superfine glass fibre partition board lead dendritic crystal, it is characterised in that：Including following Step：
    （1）Using 2 pure lead flakes as positive and negative pole plate, superfine glass fibre partition board to be measured is close between 2 lead flakes, assembles Test cell apparatus；
    （2）Constant-current charge is carried out to testing cell apparatus, survey and draw voltage-time graph, obtain Time value；
    （3）Determine test magnitude of voltage of the cell apparatus in constant-current charge；
    Step（1）Specially：
    1. the pure lead flake 2 for selecting surface smooth, as the positive and negative pole plate of test battery；
    2. copper conductor is welded on into positive and negative electrode top of the plate portion lug position, and the position welded with epoxy sealing well, as electricity Source wire terminal；
    3. cutting superfine glass fibre partition board to be measured so as to which size is more bigger than positive and negative electrode board size；
    4. 10-60s in the lead-acid accumulator green plate immersion 30-40 wt% sulfuric acid solutions of 4 solidifications is taken, generates polar board surface Lead sulfate, is positioned over 5-10 min in air after taking-up, the sulphuric acid of polar board surface is fully reacted；
    5. rectangle cell body is obtained with poly (methyl methacrylate) plate, and 4 green plates after step 4. pickling is put in groove, and addition is gone Ionized water, submergence pole plate, 2 h of constant temperature at 50 DEG C take out whole pole plates, are left solution；
    6. will superfine glass fibre partition board to be measured immerse step solution 5. after take out, be placed between 2 pure lead flakes, by lead flake- After superfine glass fibre partition board-lead flake to be measured is stacked successively, it is put in transparent plastic bag, fixes on the both sides of transparent plastic bag Upper poly (methyl methacrylate) plate, adds a pressure transducer between poly (methyl methacrylate) plate and plastic bag, applies pressure to whole device；
    7. toward plastic bag, the sulfuric acid solution of 2-10wt%, the amount of solution is added to be defined by the lug for not having pole plate, assembling is surveyed Examination cell apparatus；
    Step 6. in pressure transducer be externally connected to pressure on the number display table, the pressure of applying is 20-100kPa.
  2. 2. according to claim 1 to measure the short-circuit method of lead-acid accumulator superfine glass fibre partition board lead dendritic crystal, which is special Levy and be：Step（2）Specially：
    Test cell apparatus are placed in 50 DEG C of temperature chambers, constant-current charge is carried out, the voltage-time curve of battery are surveyed and drawn, is worked as electricity When pressure declines suddenly, show on superfine glass fibre partition board, to there occurs short circuit, record from starting to charge up to time for being short-circuited Value.
  3. 3. according to claim 2 to measure the short-circuit method of lead-acid accumulator superfine glass fibre partition board lead dendritic crystal, which is special Levy and be：Described time value is to judge whether superfine glass fibre partition board is susceptible to the key parameter of short circuit.
  4. 4. according to claim 1 to measure the short-circuit method of lead-acid accumulator superfine glass fibre partition board lead dendritic crystal, which is special Levy and be：Step（3）Specially：During constant-current charge, the magnitude of voltage of test battery is determined.
  5. 5. according to claim 4 to measure the short-circuit method of lead-acid accumulator superfine glass fibre partition board lead dendritic crystal, which is special Levy and be：Described constant-current charge current value is the apparent current density and test electricity of battery pole plates in Battery formation charging process The product of the area of pond pole plate.
  6. 6. a kind of method of measurement lead-acid accumulator superfine glass fibre partition board lead dendritic crystal short circuit as claimed in claim 1 is obtained Test cell apparatus.
CN201510001788.2A 2015-01-05 2015-01-05 Method for measuring lead dendrite crystal short-circuiting of superfine glass fiber partition boards of lead-acid storage battery Expired - Fee Related CN104459561B (en)

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Publication number Priority date Publication date Assignee Title
CN105974324B (en) * 2016-05-16 2019-01-18 天能电池集团有限公司 A kind of detection method of AGM partition anti-short circuit capability
CN109060785A (en) * 2018-06-21 2018-12-21 超威电源有限公司 The test method of lead sulfate in a kind of lead storage battery separator paper

Citations (5)

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CN2859552Y (en) * 2005-11-07 2007-01-17 风帆股份有限公司 Resistance tester for accumulator separator
CN1985385A (en) * 2004-02-27 2007-06-20 日本板硝子株式会社 Separator for lead-acid battery
CN102721930A (en) * 2012-06-18 2012-10-10 江苏理士电池有限公司 Testing method for capacity of pole plate of lead-acid storage battery
CN104035036A (en) * 2014-04-29 2014-09-10 天能电池集团有限公司 Sealing valve-regulated lead-acid battery cycle life testing method
CN104155609A (en) * 2013-12-31 2014-11-19 双新电器(郑州)制造有限公司 Maintenance-free lead-acid storage battery nondestructive testing method and nondestructive testing instrument

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JP2002305038A (en) * 2001-04-05 2002-10-18 Japan Storage Battery Co Ltd Defect determining method of lead-acid battery and charging method of lead-acid battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1985385A (en) * 2004-02-27 2007-06-20 日本板硝子株式会社 Separator for lead-acid battery
CN2859552Y (en) * 2005-11-07 2007-01-17 风帆股份有限公司 Resistance tester for accumulator separator
CN102721930A (en) * 2012-06-18 2012-10-10 江苏理士电池有限公司 Testing method for capacity of pole plate of lead-acid storage battery
CN104155609A (en) * 2013-12-31 2014-11-19 双新电器(郑州)制造有限公司 Maintenance-free lead-acid storage battery nondestructive testing method and nondestructive testing instrument
CN104035036A (en) * 2014-04-29 2014-09-10 天能电池集团有限公司 Sealing valve-regulated lead-acid battery cycle life testing method

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