CN107887664A - A kind of lead-acid accumulator microcirculation formation method - Google Patents
A kind of lead-acid accumulator microcirculation formation method Download PDFInfo
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- CN107887664A CN107887664A CN201710874409.XA CN201710874409A CN107887664A CN 107887664 A CN107887664 A CN 107887664A CN 201710874409 A CN201710874409 A CN 201710874409A CN 107887664 A CN107887664 A CN 107887664A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a kind of lead-acid accumulator microcirculation formation method, belong to lead-acid accumulator manufacturing technology field.Described formation method is carried out under conditions of without recirculated water, according to the conversion situation of active material inside pole plate in formation process, by the way of combination is charged and discharged, multi-step chemical conversion.Starting stage, it is melted into using low current, since second step by the way of the charging of constant-current charge combination gradient, when constant-current charge is to a certain degree, polarize larger, microcirculation charging (short time discharge and recharge alternate cycles) is now changed into, depolarising, electric energy can be made more to change into chemical energy.Wherein the 4th step is filled with more electricity, unconverted material in pole plate is fully converted into available active material.The present invention uses multiple discharge and microcirculation charge and discharge electrical depolarization, so as to control whole formation process temperature to be no more than 45 DEG C, realizes no recirculated water chemical conversion, save cost of water treatment reduces labor intensity simultaneously.
Description
Technical field
The present invention relates to lead-acid accumulator manufacturing technology field, and in particular to a kind of lead-acid accumulator microcirculation side of being internalized into
Method.
Background technology
At present, lead-acid accumulator remains one of most widely used battery, and it is lead-acid accumulator manufacturing process to be melted into
In a step important process, the quality of chemical conversion directly affects the performance of lead-acid accumulator.
Lead-acid accumulator chemical conversion is divided into tank formation and is internalized into two ways.Because tank formation environmental pollution is larger, mesh
Preceding most of companies use green formation method.
It is usually repeatedly to be charged, discharged until chemical conversion terminates using constant current to be internalized into technology at present.Chemical conversion is generally adopted early stage
With lasting charging modes, but battery can produce amount of heat, cause electrolyte temperature to raise, moisture loss, sulfuric acid density liter
Height, formation efficiency reduces, and battery temperature is too high, can influence battery cryogenic property, and on the other hand, temperature is too high, generates sulphur
Lead plumbate crystallization is big, and polarization is big, hardly possible chemical conversion.Pulse technique can depolarize, and improve charge efficiency, but pulsing unit input is larger.
Because constant-current charge polarization is big, there is quite a few electricity to be used for decomposition water, formation process need to be filled with electricity compared with
More, the electric energy of formation process consumption is huge.Industrial production needs 96 hours or so using the constant current chemical conversion used time at present, limitation
The lifting of production capacity.
It is internalized into charging process, early stage, the lead plaster of sulphur acid and alkaline chemically reacted, and amount of heat was released, plus interior
Hinder larger, produce a large amount of Joule heats, composite factor causes battery temperature to raise rapidly, in order to prevent temperature it is too high cause it is cell performance
It can deteriorate, each producer is cooled down using recirculated water, a kind of electric power storage as disclosed in the A of patent document CN 104393323
Pond chemical synthesizing method, temperature is reduced using the circulator bath type of cooling in charging process, temperature is maintained at 8 DEG C Celsius~58 DEG C models
In enclosing.But need to increase the fund input of cooling device and recycling equipment using the type of cooling of recirculated cooling water；Separately
Outside, the water after circulation, which must be handled, reaches certain index and could use, and cost of water treatment is higher.
In view of the above-mentioned problems, exploitation one kind is without circulating water cooling, it is possible to increase the method for formation efficiency can be solved effectively
The problems such as certainly production cost is high in the prior art, production capacity is low.
The content of the invention
It is an object of the invention to provide a kind of lead-acid accumulator formation method, dropped in formation process without recirculated water
Temperature, and can enough improve formation efficiency.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of lead-acid accumulator microcirculation chemical synthesizing method, it is placed in after adding electrolyte into battery to be changed in cold bath,
Take out after battery temperature is down to 15-35 DEG C, be melted under the conditions of without recirculated water, comprised the following steps：
(1) 0.1-0.2C charges to battery tension and reaches 2.75-2.9V/ single lattices, is discharged to and reaches final voltage；
(2) 0.2-0.3C charges to 2.65-2.9V/ single lattices；Again with charging current 0.2-0.3C, discharge current 0.18-
0.12C, discharge and recharge alternate cycles carry out 8-9h, are discharged to and reach final voltage；
(3) 0.2-0.3C charges to 2.65-2.9V/ single lattices；Again with charging current 0.2-0.3C, discharge current 0.18-
0.12C, discharge and recharge alternate cycles carry out 6-7h, are discharged to and reach final voltage；
(4) 0.2-0.3C charges to 2.65-2.9V/ single lattices；Again with charging current 0.2-0.3C, discharge current 0.08-
0.12C, after discharge and recharge alternate cycles carry out 10-12h, 0.1-0.2C charging 2-3h, it is discharged to and reaches final voltage；
(5) 0.2-0.3C charges to 2.65-2.9V/ single lattices；Again with charging current 0.2-0.3C, discharge current 0.08-
0.12C, after discharge and recharge alternate cycles carry out 6-7h；0.1-0.2C chargings 1-2h；
(6) floating charge is to voltage stabilization.
After battery acid adding to be changed, inside battery acid-base reaction can produce amount of heat, cold bath can fast endothermic, keep away
Exempt from inside battery because of the too high influence active material configuration of temperature.Cold water bath temperature is 0~20 DEG C, and water temperature is unsuitable high, otherwise cools
Effect is poor, extends cold bath standing time.
Preferably, the electrolyte temperature used is no more than 15 DEG C.Electrolyte temperature is higher, adds internal heating after battery
It is faster, even if subsequently cooling internal temperature of battery is still higher.
The present invention adds electrolyte using vacuum, vacuumizes 2-6 times, is added in 0.5-3min.Cold water is statically placed in after acid adding
1-4h in bath.Taken out after battery temperature is less than 35 DEG C, at room temperature charging chemical conversion, if starting stage battery temperature is too high,
Subsequent charge process bulk temperature can be higher, is unfavorable for effective progress of chemical conversion.
The present invention is melted into step by adjusting so that battery temperature controls below 45 DEG C all the time, avoids occurring because of inside
The too high situation for causing battery performance to deteriorate of temperature.
The present invention is according to the conversion situation of active material inside pole plate in formation process, the side combined using charging and discharging
Formula, multi-step chemical conversion, charged in each step and start to discharge to a certain extent, when polarizing larger, eliminated polarization, avoid excess moisture
Loss, keeping sulfuric acid density, chemical conversion is faster in reduced levels.After electric discharge, electrode interior sulfuric acid leading crystal is smaller, activity
Height, easily dissolving, is charged using larger current constant mode, is accelerated lead sulfate and is changed into brown lead oxide, prevents generation to be difficult to what is converted
Larger sulfuric acid leading crystal.
In step (1), using low current charge.Due to being melted into initial stage, battery pole plates are substantially non-conductive, and Ohmic resistance compares
Greatly, caused Joule heat is more, and therefore, chemical conversion early stage is melted into using low current, is formed conductive material, is then carried out using larger current
Charging, can both reduce electric current heat production, can reduce the charging interval again.
Preferably, in step (1), charging is carried out in two steps, is followed successively by：0.1-0.125C chargings 5-8h, 0.15-0.2C
Charge 6-8h.
Since step (2), by the way of the charging of constant-current charge combination gradient, wherein gradient charging uses microcirculation side
Formula.When constant-current charge to 2.65-2.9V/ single lattices, polarization is larger, produces amount of heat and electrolysis water, current efficiency is low, now turns
Charged (short time discharge and recharge alternate cycles) into microcirculation, there is depolarization effect, electric energy can be made more to change into chemistry
Energy.
Preferably, in step (2)-(5), discharge and recharge alternating cyclical process in two stages, first stage：0.25C
Charge 9min, 0.1C electric discharge 1min, discharge and recharge alternate cycles；Second stage：0.15C charging 9min, 0.1C electric discharge 1min, fill
Electric discharge alternate cycles.
Electric current microcirculation again is reduced after first time microcirculation, according to Mas law, is charged using low charging modes
It is more efficient.The charging current of second of microcirculation is smaller, although the time length used, caused heat are expanded in time
Dissipate, effectively avoid temperature too high.
In step (4), more electricity is filled with, unconverted material in pole plate is fully converted into available work
Property material, on the other hand, electrolyte is reached required density, reach the voltage of requirement.
In step (4) and (5), increase low current constant-current charge after microcirculation discharge and recharge, make unconverted material in pole plate
Fully conversion, especially surface is difficult to the lead sulfate converted.
The present invention is combined using overall electric discharge and microcirculation electric discharge, and dehydration is less, and sour density rise is relatively small, chemical conversion
Speed faster, on the one hand can improve charge acceptance, on the other hand have time enough cooling, avoid internal temperature of battery
It is too high, final voltage 1.67~2V/ single lattices are discharged to every time.Preferably, in step (1)-(4), put with 0.25-0.5C constant currents
Electricity is to reaching final voltage.More preferably, in step (2)-(4), with 0.5C constant-current discharges.
Preferably, described being internalized into comprises the following steps：
(1) 0.1-0.125C chargings 5-8h, 0.15-0.2C chargings 6-8h, 0.25-0.5C electric discharge 0.5-1h；
(2) 0.25C chargings 0.5h；With 0.25C charging 9min, 0.1C electric discharges 1min, discharge and recharge alternate cycles 4.5-5h；Again
With 0.15C charging 9min, 0.1C electric discharges 1min, discharge and recharge alternate cycles 3.5-4h；0.5C electric discharges 1-1.2h；
(3) 0.25C chargings 2h；With 0.25C charging 9min, 0.1C electric discharges 1min, discharge and recharge alternate cycles 3-3.5h；Again with
0.15C charging 9min, 0.1C electric discharges 1min, discharge and recharge alternate cycles 3-3.5h；0.5C electric discharges 1.4-1.6h；
(4) 0.25C chargings 3h；With 0.25C charging 9min, 0.1C electric discharges 1min, discharge and recharge alternate cycles 2.5-3h；Again with
0.15C charging 9min, 0.1C electric discharges 1min, discharge and recharge alternate cycles 8-8.5h；0.15C chargings 2-3h；0.5C electric discharges 2-2.1h；
(5) 0.25C chargings 3h；With 0.25C charging 9min, 0.1C electric discharges 1min, discharge and recharge alternate cycles 3-3.5h；Again with
0.15C charging 9min, 0.1C electric discharges 1min, discharge and recharge alternate cycles 3-3.5h；0.15C chargings 1-2h；
(6) 0.025C chargings 1-2h, takes out acid, and chemical conversion is completed.
C refers to battery rated capacity in said process.
The beneficial effect that the present invention possesses：
(1) chemical synthesis technology of the present invention is melted into using multistep discharge and recharge, initial stage is melted into, using low current charge, by electric conductivity
Bad material is converted into conductive material, while reduces electric current heat production.
(2) multiple discharge and microcirculation charge and discharge electrical depolarization are used, so as to control temperature in formation process to raise, entirely
Formation process temperature is no more than 45 DEG C, realizes no recirculated water chemical conversion, save cost of water treatment reduces labor intensity simultaneously.Charging
Measure as 8.1-8.5 times of rated capacity, reduce chemical conversion energy consumption.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
Battery model：6-DZM-12
9 DEG C of battery acid adding temperature, acid adding density 1.250g/ml.Using vacuum acid adding machine automatical dosing, vacuum
0.05MPa, take out 5 vacuum.After acid adding, the static 2h in 10 DEG C of cooling waters, taking-up is melted at room temperature.
The first step：1.5A charging 8h, 1.8A charging 7h, 3A electric discharges 0.5h；
Second step：3A chargings 0.5h；Then 3A fills 9min, and 1.2A puts 1min, circulates 5h；3A fills 9min, and 1.2A puts 1min,
Circulate 3.5h；6A electric discharges 1h；
3rd step：3A chargings 2h；Then 3A fills 9min, and 1.2A puts 1min, circulates 3.5h；3A fills 9min, and 1.2A puts 1min,
Circulate 3.5h；6A electric discharges 1.5h；
4th step：3A chargings 3h；Then 3A fills 9min, and 1.2A puts 1min, circulates 2.5h；3A fills 9min, and 1.2A puts 1min,
Circulate 8.5h；1.8A chargings 2h；6A electric discharges 2h；
5th step：3A chargings 3h；Then 3A fills 9min, and 1.2A puts 1min, circulates 3h；3A fills 9min, and 1.2A puts 1min, follows
Ring 3h；1.8A chargings 2h；
6th step：0.3A chargings 2h takes out acid.Complete Battery formation.
Performance detection is carried out to the battery after chemical conversion, as a result as shown in table 1.
Table 1
| Technique | 2hr capacity/Ah | Voltage/V | - 15 DEG C of low temperature/min | 100%DOD/ times |
| Existing process | 12.6-13.2 | 13.25-13.30 | 94-100 | 400-500 |
| This technique | 12.6-13.2 | 13.23-13.27 | 94-100 | 450-550 |
Existing process in upper table is as follows：1st, 1.8A fills 3h, and 3A fills 7.5h, and 3.6A puts 0.5h；2nd, 3A fills 2.5h, and 3.6A is put
1h；3rd, 3A fills 3.0h, and 4.8A puts 1h；4th, 3A fills 3.5h, and 4.8A puts 1h；5th, 3A fills 4.0h, and 4.8A puts 1.25h；6th, 3A fills 4.0h,
4.8A puts 1.25h；7th, 3A fills 6.0h, and 1.8A fills 4h, and 6A puts 2h；8th, 3A fills 6.0h, and 1.2A fills 7.5h；9th, 0.2A fills 2.5h and taken out
Acid, complete Battery formation.
The existing process charging interval is grown, and formation process battery polarization is big, and caused heat is larger, it is necessary to using recirculated water cooling
But.
Embodiment 2
Battery model：6-DZM-20
9 DEG C of battery acid adding temperature, acid adding density 1.250g/ml. use vacuum acid adding machine automatical dosing, vacuum
0.05MPa, take out 5 vacuum.After acid adding, the static 2h in 10 DEG C of cooling waters, taking-up is melted at room temperature.
The first step：2.5A charging 8h, 3A charging 8h, 3A electric discharges 0.5h；
Second step：5A chargings 0.5h；Then 5A fills 9min, and 2A puts 1min, circulates 5h；5A fills 9min, and 2A puts 1min, circulation
3.5h；10A electric discharges 1h；
3rd step：5A chargings 2h；Then 5A fills 9min, and 2A puts 1min, circulates 3.5h；5A fills 9min, and 2A puts 1min, circulation
4h；10A electric discharges 1.5h；
4th step：5A chargings 3h；Then 5A fills 9min, and 2A puts 1min, circulates 2.5h；5A fills 9min, and 2A puts 1min, circulation
8.5h；3A chargings 2h；10A electric discharges 2h；
5th step：5A chargings 3h；Then 5A fills 9min, and 2A puts 1min, circulates 3h；5A fills 9min, and 2A puts 1min, circulation
3h；3A chargings 2h；
6th step：0.5A chargings 2h takes out acid.Complete Battery formation.
Performance detection is carried out to the battery after chemical conversion, as a result as shown in table 2.
Table 2
| Technique | 2hr capacity/Ah | Voltage/V | - 15 DEG C of low temperature/min | 100%DOD/ times |
| Existing process | 22.1-23.2 | 13.26-13.33 | 88-93 | 350-400 |
| This technique | 21.0-22.2 | 13.25-13.30 | 88-93 | 350-450 |
Existing process in upper table：1st, 3A fills 3h, and 5A fills 7.5h, and 6A puts 0.5h；2nd, 5A fills 2.5h, and 6A puts 1h；3rd, 5A fills
3.0h, 8A put 1h；4th, 5A fills 3.5h, and 8A puts 1h；5th, 5A fills 4.0h, and 8A puts 1.25h；6th, 5A fills 4.0h, and 8A puts 1.25h；7、5A
6.0h is filled, 3A fills 4h, and 10A puts 2h；8th, 5A fills 6.0h, and 2A fills 5.5h, and 1A fills 3h；9th, 0.2A fills 2.5h and takes out acid, completes battery
Into.
The existing process charging interval is grown, and formation process battery polarization is big, and caused heat is larger, it is necessary to using recirculated water cooling
But.
Claims (7)
1. a kind of lead-acid accumulator microcirculation formation method, it is characterised in that it is rearmounted that electrolyte is added into battery to be changed
In cold bath, take out after battery temperature is down to 15-35 DEG C, be melted under conditions of without recirculated water, including following step
Suddenly：
(1) 0.1-0.2C charges to battery tension and reaches 2.75-2.9V/ single lattices, is discharged to and reaches final voltage；
(2) 0.2-0.3C charges to 2.65-2.9V/ single lattices；Again with charging current 0.2-0.3C, discharge current 0.18-0.12C,
Discharge and recharge alternate cycles carry out 8-9h, are discharged to and reach final voltage；
(3) 0.2-0.3C charges to 2.65-2.9V/ single lattices；Again with charging current 0.2-0.3C, discharge current 0.18-0.12C,
Discharge and recharge alternate cycles carry out 6-7h, are discharged to and reach final voltage；
(4) 0.2-0.3C charges to 2.65-2.9V/ single lattices；Again with charging current 0.2-0.3C, discharge current 0.08-0.12C,
After discharge and recharge alternate cycles carry out 10-12h, 0.1-0.2C charging 2-3h, it is discharged to and reaches final voltage；
(5) 0.2-0.3C charges to 2.65-2.9V/ single lattices；Again with charging current 0.2-0.3C, discharge current 0.08-0.12C,
After discharge and recharge alternate cycles carry out 6-7h；0.1-0.2C chargings 1-2h；
(6) floating charge is to voltage stabilization.
2. lead-acid accumulator microcirculation formation method as claimed in claim 1, it is characterised in that the electrolyte temperature of use
No more than 15 DEG C.
3. lead-acid accumulator microcirculation formation method as claimed in claim 2, it is characterised in that vacuumize and add electrolyte,
Added in 0.5-3min.
4. lead-acid accumulator microcirculation formation method as claimed in claim 1, it is characterised in that in step (1), in two steps
Charged, be followed successively by：0.1-0.125C charging 5-8h, 0.15-0.2C chargings 6-8h.
5. lead-acid accumulator microcirculation formation method as claimed in claim 1, it is characterised in that in step (2)-(5), fill
Alternating cyclical process discharge in two stages, first stage：0.25C charging 9min, 0.1C electric discharge 1min, charge and discharge electrical alternations follow
Ring；Second stage：0.15C charging 9min, 0.1C electric discharge 1min, discharge and recharge alternate cycles.
6. lead-acid accumulator microcirculation formation method as claimed in claim 1, it is characterised in that in step (1)-(4), with
0.25-0.5C constant-current discharges are to reaching final voltage.
7. lead-acid accumulator microcirculation formation method as claimed in claim 1, it is characterised in that chemical conversion includes following step
Suddenly：
(1) 0.1-0.125C chargings 5-8h, 0.15-0.2C chargings 6-8h, 0.25-0.5C electric discharge 0.5-1h；
(2) 0.25C chargings 0.5h；With 0.25C charging 9min, 0.1C electric discharges 1min, discharge and recharge alternate cycles 4.5-5h；Again with
0.15C charging 9min, 0.1C electric discharges 1min, discharge and recharge alternate cycles 3.5-4h；0.5C electric discharges 1-1.2h；
(3) 0.25C chargings 2h；With 0.25C charging 9min, 0.1C electric discharges 1min, discharge and recharge alternate cycles 3-3.5h；Again with
0.15C charging 9min, 0.1C electric discharges 1min, discharge and recharge alternate cycles 3-3.5h；0.5C electric discharges 1.4-1.6h；
(4) 0.25C chargings 3h；With 0.25C charging 9min, 0.1C electric discharges 1min, discharge and recharge alternate cycles 2.5-3h；Again with
0.15C charging 9min, 0.1C electric discharges 1min, discharge and recharge alternate cycles 8-8.5h；0.15C chargings 2-3h；0.5C electric discharges 2-2.1h；
(5) 0.25C chargings 3h；With 0.25C charging 9min, 0.1C electric discharges 1min, discharge and recharge alternate cycles 3-3.5h；Again with
0.15C charging 9min, 0.1C electric discharges 1min, discharge and recharge alternate cycles 3-3.5h；0.15C chargings 1-2h；(6) 0.025C chargings 1-
2h, takes out acid, and chemical conversion is completed.
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Cited By (5)
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| CN109546249A (en) * | 2018-12-17 | 2019-03-29 | 江苏聚合新能源科技有限公司 | A kind of chemical synthesizing method and device of lead-acid battery |
| CN109755667A (en) * | 2019-01-11 | 2019-05-14 | 天能电池集团有限公司 | A kind of lead storage battery rapid forming method |
| CN111092270A (en) * | 2019-11-29 | 2020-05-01 | 天能电池集团股份有限公司 | Lead storage battery formation process optimization method |
| CN112331943A (en) * | 2020-11-04 | 2021-02-05 | 浙江天能电池(江苏)有限公司 | Formation, screening and matching process for power lead storage battery |
| CN114361609A (en) * | 2021-12-10 | 2022-04-15 | 安徽力普拉斯电源技术有限公司 | High-temperature-resistant acid adding process for container formation of power battery |
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| CN114361609A (en) * | 2021-12-10 | 2022-04-15 | 安徽力普拉斯电源技术有限公司 | High-temperature-resistant acid adding process for container formation of power battery |
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