CN105428603B - A kind of curing process of lead-acid battery negative pole plate - Google Patents
A kind of curing process of lead-acid battery negative pole plate Download PDFInfo
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- CN105428603B CN105428603B CN201510808607.7A CN201510808607A CN105428603B CN 105428603 B CN105428603 B CN 105428603B CN 201510808607 A CN201510808607 A CN 201510808607A CN 105428603 B CN105428603 B CN 105428603B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
- H01M4/21—Drying of pasted electrodes
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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
The invention discloses a kind of curing process of lead-acid battery negative pole plate, the curing process includes aoxidizing and dries two stages, and oxidation stage comprises the following steps：Initial step：50 DEG C are maintained the temperature at, relative humidity is not less than 98%, 35 hours time；Heat up wet down step：Kept for 35 hours after 35 DEG C of heating every time, reduction relative humidity 2% 4%, heating wet down, be finally warming up to 60 DEG C；Heat up cooling step：First heat up, every time 5 10 DEG C of heating, kept for 48 hours after heating, be increased to 75 DEG C of maximum temperature, then cool, every time 35 DEG C of cooling, kept for 35 hours after cooling, minimum to be down to 65 DEG C, this step keeps humidity to be not less than 95%.The present invention passes through Optimizing Process Parameters, it is ensured that in shortest time internal oxidition, plate active material crystallization effect preferably, plate strength is obviously improved pole plate, burst scrappage reduction nearly 1%, and the curing process time foreshortens to two days.
Description
Technical field
Field is manufactured the present invention relates to lead-acid accumulator, and in particular to a kind of curing process of lead-acid battery negative pole plate.
Background technology
In lead-acid accumulator manufacturing process, polar plate solidification is one of essential core, and grid only passes through after lead plaster is filled
Curing process, can just make lead plaster particle mutually be linked to form continuous solid skeleton, and be tightly attached on grid.Pole plate is consolidated
The quality of change directly affects battery performance index, service life, and current pole plate outstanding problem is poor plate strength, pole plate index one
The problems such as cause property difference.
Polar plate solidification is divided into oxidation and dries two stages.Oxidizing process is mainly completed：(1) oxidation of free lead, is improved
The capacity of active material；(2) oxidation of grid rib surface lead, the adhesion between increase grid muscle and active material；(3) alkali
The recrystallization of formula lead sulfate, improves the intensity of pole plate.Drying process mainly completes the drying of pole plate, enhancing plate strength and formation
Porous electrode.
Green plate solidification is a highly important process during lead-acid storage battery production, controls solidification temperature, phase
It is the key of green plate curing process to humidity and hardening time.If the control not yet in effect of these parameters, green plate after solidification
In active material in will be difficult to the tribasic lead sulfate and four basic lead sulphate mixtures that obtain optimal proportion.
Free lead content after solidification in pole plate will drop to less than 5%, preferably no more than 1%, and this part free lead is only
Active material can be just transformed into by being oxidized to after lead oxide.Due to Pb, (density is 11.34g/cm3)→PbSO4(density is
6.32g/cm3)→PbO2(density is 9.37g/cm3) conversion process in Volume Changes it is very big, by existing curing process solidify
Pole plate afterwards can cause plate buckling, active material to take off in formation process because pole plate internal volume expands the stress produced
Fall.Simultaneously because the increase of active material volume, can make the porosity of active material reduces, and causes what positive plate was produced when being melted into
Oxygen is not allowed to be readily transferred to polar board surface and overflow, and produces pressure, this oxygen with pressure in pole plate inner accumulation
The resistance of liquid, has souring from space is overcome inside pole plate when being moved to polar board surface, causes active material to come off,
Shorten the service life of battery.
The major defect of analysis conventional curing mode：(1) polar plate solidification disposing way is flatwise, between pole plate and pole plate
Spacing is smaller, and oxygen releases heat hardly possible exclusion into slow, pole board oxidation is transmitted, and causes pole board oxidation speed slow.(2) due to itself
Battery design demand, negative plate thinner thickness, in solidification drying process, because disposing way is unreasonable, solidification temperature is high, easily
Cause plate buckling.(3) curing room internal polar plate upper, middle and lower, left and right, it is preceding in after pole plate in each cure stage, percentage of water loss and free
Lead content gap is big, and plate strength does not reach technological requirement, causes scrappage high.(4) solidification is long arid cycle, influences curing room
Turnover, reduces production efficiency.
At present, many producers propose high temperature curing process technology, can greatly shorten the process time, but existing high temperature is solid
It is not high to there is active material bond strength in the pole plate that chemical industry skill makes, the problem of service life is short.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of curing process of lead-acid battery negative pole plate, by excellent
Change the technological parameter of oxidation stage, not only shorten the curing process cycle, and improve the bond strength of plate active material.
A kind of curing process of lead-acid battery negative pole plate, green plate is vertically hung and is placed in curing room, adjacent life
There is gap, the curing process includes aoxidizing and dries two stages, and oxidation stage comprises the following steps between pole plate：
Initial step：Keep solidification indoor temperature at 50 DEG C, relative humidity is not less than 98%, time 3-5 hour；
Heat up wet down step：3-5 DEG C of heating every time, is kept for 3-5 hours after reducing relative humidity 2%-4%, heating wet down,
Finally it is warming up to 60 DEG C；
Heat up cooling step：First heat up, every time 5-10 DEG C of heating, kept for 4-8 hours after heating, be increased to maximum temperature 75
DEG C, then cool, every time 3-5 DEG C of cooling, kept for 3-5 hours after cooling, minimum to be down to 65 DEG C, this step keeps humidity to be not less than
95%.
Green plate is vertically hung, makes that there is gap, such arrangement modes of emplacement, it is ensured that every between adjacent green plate
Green plate can be sufficiently uniformly with oxygen, moisture, and the heat that green plate oxidation discharges is evenly effectively lost.Pole plate
Between will not stick together or flexural deformation, it is ensured that pole plate indices uniformity.
To avoid in oxidation or drying process, cause regional area humiture too low or too high because pole plate spacing is too small, or
Person causes air in local area circulation not smooth, preferably, the gap of the adjacent plate is 5-10mm.
Because pole plate can be aoxidized in itself, substantial amounts of heat is released, in order to avoid green plate has just enter into curing room because of mistake
Water is too fast, causes polar board surface to ftracture, when curing process is initial, is humidified using atomized water, steam humidification, and circulating fan is transported at a high speed
Turn so that keep high humility in whole curing room.Starting stage keeps circulating fan to run at high speed, it is preferred that rotating speed is 90%
More than, humiture is consistent with curing room between principal security pole plate.
60 DEG C are warming up to from 50 DEG C, the relative humidity of environment is reduced, the dehydration of pole plate can be accelerated, preferably, heating
After wet down in pole plate water content control 7~9%.When in pole plate lead plaster keep 7% or so moisture content when, reach free lead oxidation and
The optimum condition of grid surface corrosion.
Final step is basic lead sulphate recrystallization process, the recrystallization of basic lead sulphate will be 5 in pole plate water content~
Could significantly it be carried out under conditions of 6%, tribasic lead sulfate and four basic lead sulphates are the filamentary structure being cross-linked with each other, to pole
The intensity of plate plays an important role, thus green plate must keep water content in a long time 5% in the curing process
More than.Preferably, in heating cooling step, water content control is more than 5% in pole plate.
75 DEG C are increased to again with temperature, and the active material in lead plaster generates more four basic lead sulphates, improves
The intensity of pole plate.Now, high temperature, high humidity are in curing room, in order to reduce polar board surface moisture evaporation, air circulation is unsuitable
Excessive, circulating fan rotating speed control 40% or so can uniformly moisturizing, insulation.
Preferably, being kept for 4 hours every time after heating wet down.
Preferably, in heating cooling step, 5 DEG C of cooling every time is kept for 4 hours every time after cooling；It is warming up to the highest temperature
75 DEG C of degree, is kept for 8 hours.
Preferably, the oxidation stage comprises the following steps：
(a) temperature 50 C, relative humidity 98%, time 4h in curing room are kept；
(b) 55 DEG C are warming up to, reduction relative humidity keeps 4h to 95%；
(c) 60 DEG C are warming up to, reduction relative humidity keeps 4h to 92%；
(d) 70 DEG C are warming up to, relative humidity is improved to 96%, and keep 4h；
(e) 75 DEG C are warming up to, relative humidity is improved to 98%, and keep 8h；
(f) 70 DEG C are cooled to, maintains relative humidity constant, and keep 4h；
(g) 65 DEG C are cooled to, maintains relative humidity constant, and keep 4h.
Using the curing process, the oxidation stage used time is only 32 hours.
Wherein, step (a) is initial step, using the condition of low temperature and high relative humidity, is to prevent green plate dehydration too fast, make
Into polar board surface cracking.
Step (b)-(c) is heating wet down step, can accelerate the dehydration of pole plate so that the control of pole plate moisture is left 7%
The right side, now the oxidation rate of pole plate is relative reaches peak, can improve the crystallizing power of plate active material.
Step (d)-(g) is heating cooling step so that active material generates more four alkali formula sulfuric acid in crystallization process
Lead, so as to obtain the tribasic lead sulfate and four basic lead sulphate mixtures of optimal proportion.In order to prevent in temperature lifting process
Middle pole plate moisture evaporation is too fast, causes pole board oxidation not thorough and cracks, it is necessary to keep high- humility state, and extension pole plate is lived
The property substance crystallization cycle.
In the curing process of the present invention, drying stage comprises the following steps：Progressively heat up wet down, makes relatively wet in curing room
Degree is equal to 0%, then is warming up to 80 DEG C, maintains 5-10 hour, is finally cooled to 60 DEG C, maintenance 1-2 hours.
In order to prevent entering after drying program, moment is lost in moisture in a short time in pole plate, and the stability to pole plate is made
Into influence, using the method for gradually reducing envionmental humidity.
It is that free lead aoxidizes most fierce most complete process in initial stage of drying, when green plate aqueous active substance amount exists
During 2-5%, green plate surface vaporization speed is accelerated, and is beaten the capillary in the quick dehydration of green plate, active material and space
Logical, substantial amounts of oxygen, which can enter, participates in reaction in space.Therefore, the air circulation in this stage is the key for controlling oxidation rate,
The present invention uses 100% rotating speed.
Preferably, the drying stage comprises the following steps：
(a) 70 DEG C are warming up to, relative humidity is reduced to 80%, and maintain 2 hours；
(b) 75 DEG C are warming up to, relative humidity is reduced to 50%, and maintain 2 hours；
(c) 80 DEG C are warming up to, relative humidity is reduced to 0%, and maintain 10 hours；
(d) 60 DEG C are cooled to, is maintained 2 hours.
Step (c) is the process that is dehydrated completely of green plate, is also that tribasic lead sulfate in lead plaster is converted into four alkali formula sulphur
The critical stage of lead plumbate, therefore, its temperature, time control are crucial.The water content of last obtained negative plate to control≤
0.5%.
16 hours drying stage used times of this scheme.
The beneficial effect that the present invention possesses：(1) green plate is by the way of vertically hanging, the spacing between increase pole plate,
Oxygen input, heat are scattered and disappeared uniformly effectively, make obtained pole plate indices stable and consistent；(2) present invention is solidified by optimizing
Technological parameter, it is ensured that in shortest time internal oxidition, plate active material crystallization effect preferably, plate strength is obviously improved pole plate,
Burst scrappage reduction nearly 1%；(3) the curing process time foreshortens to two days, improving production efficiency.
Embodiment
Technical scheme is described in detail with reference to specific embodiment, but following embodiments are only only this
The preferred embodiment of invention, and it is not all.Based on the embodiment in embodiment, those skilled in the art are not making creation
Property work on the premise of obtain other embodiments, belong to protection scope of the present invention.
Comparative example 1
1st, pole plate is solidified using traditional curing process, comprised the following steps：
(1) green plate is flat on and dried on frame；
(2) solidify and dry, each stage parameter such as table 1.
Table 1
Note：Circulating fan is rotated by fan and air circulation is produced in curing room in table 1, allows regional in curing room
Humidity is consistent；Relative humidity is mainly adjusted by solidifying the atomized water humidifying spraying nozzle water spray of indoor location, also may be used in addition
To increase steam direct-injection program adjustment relative humidity.
2nd, detect
Free lead content and pole plate mechanical strength on Detection electrode at 15 random test points.Free lead testing result is such as
Shown in table 2, pole plate mechanical strength testing result is as shown in table 3.
Table 2
The negative plate free lead content as made from the detection data of table 2 find out conventional method meets lead-acid accumulator industry
It is required that.But wherein the test point of free lead content >=3.5% is more than 29%.
Table 3
Found out by the detection data of table 3, accumulator negative plate made from conventional method all has cream in strength test
Phenomenon, wherein having 1 piece more than 1%, is detected unqualified.
Embodiment 1
1st, it is a kind of to improve the curing process of accumulator negative plate quality, comprise the following steps：
(1) green plate is vertically hung, the spacing between two green plates is maintained at more than 5mm；
(2) solidify and dry, each stage parameter such as table 4.
Table 4
Note：By adjusting humidity to curing room jet atomization water, increase steam directly spray device, it is ensured that when temperature is raised, adjust
Save humidity；Air is sprayed into curing room, it is ensured that indoor oxygen is supplied.The 8th stage started drying process in table 4, circulating fan
Rotating speed reaches maximum, accelerates hydrofuge.
The curing process whole flow process of the present embodiment needs 48 hours, more time-consuming than comparative example 1 to shorten within 70 hours 22 hours,
Greatly improve the turnover rate of curing room, improving production efficiency.
2nd, detect
Free lead content and pole plate mechanical strength on Detection electrode at 15 random test points.Free lead testing result is such as
Shown in table 5, pole plate mechanical strength testing result is as shown in table 6.
Table 5
Accumulator negative plate overwhelming majority test point is free as made from the detection data of table 5 can be seen that the present embodiment
Lead content≤3.5%, is compared with the data of comparative example 1, and pole plate free lead content is substantially reduced made from the present embodiment, shows solid
The quality for changing obtained accumulator negative plate after process modification significantly improves.
Table 6
Do not fall substantially in the accumulator negative plate intensity detection as made from the detection data of table 6 can be seen that the present embodiment
Cream, is compared with the data of comparative example 1, shows that the mechanical strength of obtained accumulator negative plate after curing process improvement significantly increases
Plus.
Claims (9)
1. a kind of curing process of lead-acid battery negative pole plate, green plate is vertically hung and is placed in curing room, adjacent plate
Between have gap, the curing process include aoxidize and dry two stages, it is characterised in that oxidation stage include following step
Suddenly：
Initial step：Keep solidification indoor temperature at 50 DEG C, relative humidity is not less than 98%, time 3-5 hour；
Heat up wet down step：3-5 DEG C of heating every time, reduces holding 3-5 hours after relative humidity 2%-4%, heating wet down, finally
It is warming up to 60 DEG C；
Heat up cooling step：First heat up, every time 5-10 DEG C of heating, kept for 4-8 hours after heating, be increased to 75 DEG C of maximum temperature,
Then cool, every time 3-5 DEG C of cooling, kept for 3-5 hours after cooling, minimum to be down to 65 DEG C, this step keeps humidity to be not less than
95%；
Drying stage comprises the following steps：Progressively heat up wet down, solidification indoor relative humidity is equal to 0%, then is warming up to 80 DEG C,
Maintain 5-10 hours, be finally cooled to 60 DEG C, maintain 1-2 hours.
2. curing process as claimed in claim 1, it is characterised in that the gap of the adjacent plate is 5-10mm.
3. curing process as claimed in claim 1, it is characterised in that kept for 4 hours every time after heating wet down.
4. curing process as claimed in claim 1, it is characterised in that after heating wet down in pole plate water content control 7~
9%.
5. curing process as claimed in claim 1, it is characterised in that 5 DEG C of cooling every time, is kept for 4 hours every time after cooling.
6. curing process as claimed in claim 1, it is characterised in that in heating cooling step, be warming up to 75 DEG C of maximum temperature,
Kept for 8 hours.
7. curing process as claimed in claim 1, it is characterised in that in heating cooling step, water content control exists in pole plate
More than 5%.
8. curing process as claimed in claim 1, it is characterised in that the oxidation stage comprises the following steps：
(a) temperature 50 C, relative humidity 98%, time 4h in curing room are kept；
(b) 55 DEG C are warming up to, reduction relative humidity keeps 4h to 95%；
(c) 60 DEG C are warming up to, reduction relative humidity keeps 4h to 92%；
(d) 70 DEG C are warming up to, relative humidity is improved to 96%, and keep 4h；
(e) 75 DEG C are warming up to, relative humidity is improved to 98%, and keep 8h；
(f) 70 DEG C are cooled to, maintains relative humidity constant, and keep 4h；
(g) 65 DEG C are cooled to, maintains relative humidity constant, and keep 4h.
9. curing process as claimed in claim 1, it is characterised in that the drying stage comprises the following steps：
(a) 70 DEG C are warming up to, relative humidity is reduced to 80%, and maintain 2 hours；
(b) 75 DEG C are warming up to, relative humidity is reduced to 50%, and maintain 2 hours；
(c) 80 DEG C are warming up to, relative humidity is reduced to 0%, and maintain 10 hours；
(d) 60 DEG C are cooled to, is maintained 2 hours.
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| CN201510808607.7A CN105428603B (en) | 2015-11-19 | 2015-11-19 | A kind of curing process of lead-acid battery negative pole plate |
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| CN201510808607.7A CN105428603B (en) | 2015-11-19 | 2015-11-19 | A kind of curing process of lead-acid battery negative pole plate |
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| CN105428603B true CN105428603B (en) | 2017-10-31 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108232123B (en) * | 2017-12-26 | 2020-05-12 | 浙江天能动力能源有限公司 | Curing process for positive plate of lead-acid storage battery for electric automobile |
| CN109065846B (en) * | 2018-07-28 | 2020-09-22 | 河南超威电源有限公司 | Process for curing positive electrode plate of lead-acid storage battery |
| CN109742329B (en) * | 2018-11-28 | 2020-08-25 | 浙江天能动力能源有限公司 | Curing process for positive plate of storage battery |
| CN110797510A (en) * | 2019-12-06 | 2020-02-14 | 安徽轰达电源有限公司 | Negative plate curing process for storage battery production |
| CN111697202B (en) * | 2020-06-24 | 2021-10-26 | 浙江天能电池(江苏)有限公司 | Process for rapidly curing and drying negative green plate |
| CN112201775B (en) * | 2020-09-16 | 2021-12-21 | 超威电源集团有限公司 | Curing process for rapidly reducing content of free lead in green plate |
| CN113506859B (en) * | 2021-07-08 | 2022-04-26 | 江苏理士电池有限公司 | Curing and drying method for long-life valve-regulated lead-acid storage battery wet lead plaster polar plate |
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| JP5938254B2 (en) * | 2012-03-30 | 2016-06-22 | 古河電池株式会社 | Negative electrode plate for lead acid battery, method for producing the same and lead acid battery |
| CN103762340B (en) * | 2014-01-14 | 2015-09-09 | 天能集团江苏科技有限公司 | A kind of lead-acid accumulator green plate quick high-temp curing and dying process |
| CN104600255B (en) * | 2014-12-30 | 2017-01-04 | 浙江天能动力能源有限公司 | A kind of curing process of polar plate of lead acid storage battery |
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