CN109148815A - A kind of long-life lead storage battery acid adding chemical synthesizing method - Google Patents
A kind of long-life lead storage battery acid adding chemical synthesizing method Download PDFInfo
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- CN109148815A CN109148815A CN201810790806.3A CN201810790806A CN109148815A CN 109148815 A CN109148815 A CN 109148815A CN 201810790806 A CN201810790806 A CN 201810790806A CN 109148815 A CN109148815 A CN 109148815A
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000000126 substance Substances 0.000 title claims description 77
- 230000002194 synthesizing effect Effects 0.000 title claims description 15
- 239000002253 acid Substances 0.000 claims abstract description 134
- 230000005484 gravity Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 61
- 239000003792 electrolyte Substances 0.000 claims description 12
- 230000005611 electricity Effects 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 229910006529 α-PbO Inorganic materials 0.000 abstract description 5
- 239000007774 positive electrode material Substances 0.000 abstract description 4
- 230000010287 polarization Effects 0.000 abstract description 2
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 8
- 229910006531 α-PbO2 Inorganic materials 0.000 description 7
- 239000011149 active material Substances 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011555 saturated liquid Substances 0.000 description 5
- 239000011265 semifinished product Substances 0.000 description 5
- 238000009434 installation Methods 0.000 description 4
- 229910006654 β-PbO2 Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000011505 plaster Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
-
- 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
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
本发明公开了一种长寿命铅蓄电池加酸化成方法，包括以下步骤：(1)第一次加酸，向待加酸铅蓄电池中加入密度为1.05～1.25g/cm3的低比重硫酸溶液，加入体积为铅蓄电池饱和吸酸量的90％～105％；(2)第一阶段化成，充电，充电总电量为3.5C～5.0C；(3)第二次加酸，加入密度为1.25～1.65g/cm3的高比重硫酸溶液，加满；(4)第二阶段化成，先放电后再充电，放电深度为25％～80％，充电总电量为3.5C～5.0C；(5)抽净余酸。本发明通过分两次加酸，有效提升正极活性物质α‑PbO2/β‑PbO2比值，从而延长电池使用寿命，同时还可有效的降低极化提升化成效率，缩短化成周期。The invention discloses a method for forming a long-life lead storage battery by adding acid, comprising the following steps: (1) adding acid for the first time, adding a low specific gravity sulfuric acid solution with a density of 1.05-1.25 g/cm 3 to the lead storage battery to be added acid , the added volume is 90% to 105% of the saturated acid absorption of the lead-acid battery; (2) The first stage is formed, charged, and the total charge is 3.5C to 5.0C; (3) The second acid is added, and the added density is 1.25 ～1.65g/cm 3 of high specific gravity sulfuric acid solution, fill up; (4) The second stage is formed, first discharge and then charge, the depth of discharge is 25% to 80%, and the total charge is 3.5C to 5.0C; (5 ) to extract the residual acid. The invention effectively improves the ratio of the positive active material α-PbO 2 /β-PbO 2 by adding acid twice, thereby prolonging the service life of the battery, and at the same time, it can effectively reduce the polarization, improve the formation efficiency, and shorten the formation period.
Description
Technical field
The present invention relates to lead storage battery production technical fields, more particularly to a kind of long-life lead storage battery acid adding chemical conversion side
Method.
Background technique
Lead storage battery has the history in more than 150 years, and wide range of applications so far.In recent years, electric vehicle with its compared with
Good performance of riding instead of walk, lower storage space requirement and outstanding price advantage is grown rapidly in China, has benefited from this, battery
Industry is also rapidly developed.
Lead storage battery belongs to reversible dc power supply, chemical energy can be changed into electric energy, while can also converting electrical energy into
Learn energy.Lead storage battery is mainly made of electrolyte, slot cover and pole group, and the electrolyte of lead storage battery is sulfuric acid solution, wherein pole
Group is mainly made of positive plate, negative plate and partition, and partition primarily serves storage electrolyte, and the gas compound as oxygen is logical
Road, play prevent active material fall off and positive and negative electrode between short-circuit effect.
Charging process converts electrical energy into chemical energy and is stored in active material；When electric discharge, it will be stored in active material
Chemical energy be converted into electric energy.When charging, positive plate lead paste is converted to brown lead oxide, and the lead plaster on negative plate is converted to spongy
Lead, the sulfuric acid components in lead plaster are discharged into electrolyte, and the sulfuric acid concentration in electrolyte is continuously increased, and cell voltage rises, product
Accumulation of energy amount；When the cell is discharged, positive plate active material is converted to lead sulfate, and positive and negative pole active matter is also translated into lead sulfate,
And the sulfuric acid in Electolyte-absorptive, the sulfuric acid concentration in electrolyte constantly reduce, cell voltage decline, battery externally exports energy
Amount.
Charging chemical conversion is one of the critical process for influencing battery performance in lead-acid battery production technology.When chemical conversion, have
Extremely complex chemical conversion object inversion of phases process, the α-PbO of positive electrode material2With β-PbO2Ratio is always industry hot spot of interest
How problem creates α-PbO2Build environment promotes α-PbO2With β-PbO2Ratio, and while being able to satisfy initial performance, promotes the circulation longevity
Life is the target pursued.
The Chinese invention patent of Publication No. CN101673843A discloses a kind of lead-acid battery formation method, including electricity
Pond assembling, gives electrification at step at electrolyte filling, close by preparing under the conditions of 25 DEG C in electrolyte filling step after improvement
Degree is 1.200-1.300g/cm3Dilute sulfuric acid electrolyte, be initially cooled to 5-20 DEG C, then again quantify dilute sulfuric acid after cooling
Acid filling is put into cooling circulating water after acid filling and carries out water-bath cooling.And carried out in battery acid filling 1.5 hours to electrification at.
The Chinese invention patent of Publication No. CN102315489A discloses a kind of colloid battery for electric vehicle chemical conversion side
Method, for solving the problems, such as that colloid battery for electric vehicle is internalized into that time-consuming, the production cycle is long.It is filled the method includes multiple
Discharge step and twice vacuum step, wherein first time vacuum step are as follows: the battery for having filled mix acid liquor is shelved 0.5
Hour, vacuumize for the first time, vacuum degree is 0.06Mpa~0.08Mpa, and the pumpdown time is 5~8s；It vacuumizes for the second time
Carry out after the primary electric discharge of charging twice: the pumpdown time is 2~5s, and vacuum degree is 0.06Mpa~0.08Mpa.
In the prior art it is typically all first acid adding, is melted into again after standing a period of time after the completion of acid adding, it is existing to ask
Topic is positive plate early stage to be easy argillization, and battery life is partially short.
Summary of the invention
The present invention for positive plate of lead storage battery substance early stage argillization in the prior art, the service life is short the problems such as, provide one
Kind long-life lead storage battery acid adding chemical synthesizing method.
A kind of long-life lead storage battery acid adding chemical synthesizing method, comprising the following steps:
(1) first time acid adding, it is 1.05~1.25g/cm that density is added into acid lead batteries to be added3Low-gravity sulfuric acid
Solution, it is that lead storage battery saturation inhales the 90%~105% of acid amount that volume, which is added,；
(2) first stage is melted into, charging, and charging total electricity is 3.5C~5.0C；
(3) second of acid adding, addition density are 1.25~1.65g/cm3High specific gravity sulfuric acid solution, fill it up with；
(4) second stage is melted into, and is first discharged and is recharged afterwards, and depth of discharge is 25%~80%, and charging total electricity is 3.5C
~5.0C；
(5) spent acid is pumped.
Saturation inhales acid solution amount needed for the pole group part sufficiently absorption acid solution referred in battery is measured and (be saturated liquid absorption amount) to acid, adds
After entering the low-gravity sulfuric acid solution that 100% volume saturation inhales acid amount, pole group, which is substantially at, sufficiently draws acid solution state, and in battery
Be free on the spent acid except the group of pole does not have substantially.When first time acid adding, if 90% of acid adding volume lower than saturation liquid absorption amount,
Pole group is internal in being on the verge of dry state, and dehydration meeting when chemical conversion is in dry state ion is caused to pass so that being melted into the middle and later periods
Defeated to be obstructed, temperature rise is too fast to cause chemical conversion abnormal.Therefore first time acid adding amount is not lower than and is saturated the 90% of liquid absorption amount.Meanwhile in order to
Reduce formation process in dehydration, to battery carry out it is valve-control sealed after again to electrification at.
It is filled it up with described in step (3) after referring to addition high specific gravity sulfuric acid solution, other than in addition to pole, group sufficiently draws acid solution, electricity
Remaining spare space of pond is also completely filled with acid solution.After spent acid described in step (5) refers to chemical conversion, it is free on except the group of pole
Acid solution.
Preferably, the density of low-gravity sulfuric acid solution is 1.10~1.20g/cm in step (1)3。
Preferably, in step (1) low-gravity sulfuric acid solution volume be lead storage battery saturation inhale acid amount 95%~
100%.
Preferably, the density of high specific gravity sulfuric acid solution is 1.35~1.50g/cm in step (3)3。
Preferably, after the completion of acid adding chemical conversion, the final densities for controlling electrolyte are 1.34~1.38g/cm3.Formation process
In, moisture has part evaporation in battery, so the density of acid solution be increased before being relatively melted into after chemical conversion, second acid adding
The case where high specific gravity sulfuric acid solution, density and additional amount are to first time acid adding is related, in the low-gravity for determining first time acid adding
After the density and addition volume of sulfuric acid solution, according to the density of acid solution needed for final battery, by testing available second
The substantially required density of the high specific gravity sulfuric acid solution of acid adding.
Preferably, it is vacuumized after second of acid adding 2~4 times, vacuum degree is -0.06~-0.1MPa.It is taken out after second of acid adding
The purpose of vacuum is to be sufficiently mixed acid solution uniformly.What vacuum degree negative value represented is negative pressure.
Preferably, acid is taken out using electrification when pumping spent acid in step (5), electrification is filled when taking out acid with electric current 0.01C~0.02C
Electricity.Such as common 6-DZM-20 battery, rated capacity 20AH, then the sour electric current of corresponding pumping is 0.2A~0.4A.
Preferably, in first stage chemical conversion and second stage chemical conversion, charging is all made of constant-current charge, and current density is
2.5mA/cm2~7.5mA/cm2。
It is further preferred that the density of charging current is 5mA/cm in first stage chemical conversion and second stage chemical conversion2。
Preferably, after first time acid adding, first stage chemical conversion is carried out again after standing 0.5~1.5h.
Long-life lead storage battery acid adding chemical synthesizing method of the invention is added for the first time by way of quantitative acid dosing twice and chemical conversion
The dilute sulfuric acid for entering low-density through pickling, carries out second of acid adding and chemical conversion, in the electrolyte of low-density again after chemical conversion a period of time
In, pole plate pickling heating and reaction are more uniform, also promote chemical conversion is more conducive to α-PbO early period2Generation and generate the period more
It is long, α-PbO2//β-PbO2Ratio comparison, which just has, to be obviously improved.By acid adding in two times, α-PbO is created2Growth
Environment effectively promotes positive active material α-PbO2/β-PbO2Ratio, to extend battery, while can also be effective
It reduces polarization and promotes formation efficiency, shorten the chemical conversion period.
Specific embodiment
Embodiment 1
6-DZM-20 battery semi-finished product are taken, acid adding and chemical conversion are carried out using the method for the present invention, sample making course is as follows:
1) first time acid adding, it is 1.05g/cm that density is added into acid lead batteries to be added3Sulfuric acid solution, acid adding volume
148ml (single lattice is saturated liquid absorption amount in 163~165ml, be saturation inhale acid amount 90% or so), using vacuum acid feeding mode into
Row, vacuum degree -0.08MPa, vacuum 1~2 time.
2) behind battery standing 1 hour completed first time acid adding, installation safety valve simultaneously opens first stage chemical synthesis technology,
With 3.6A (current density 5mA/mm2) constant-current charge 21h (charge volume 75.6Ah, 3.78C).
3) after first stage chemical conversion, battery is subjected to second of acid adding, (vacuum is carried out using vacuum acid feeding mode
Degree -0.08MPa, vacuum 2~4 times), sour density is 1.65g/ml, and acid adding volume is 62ml.The determination and chemical conversion of battery acid adding amount
Total fluid loss and aggregate demand are related, need to be weighed to obtain dehydration data to the battery weight of each process when determining technique
Total acid adding volume and the acid adding volume in two stages are determined afterwards, and 6-DZM-20 is needed using the total acid adding volume of technology of the invention
Seeking Truth 210mL, therefore the acid adding volume of second stage is 210-148=62mL.
4) before second stage chemical conversion is opened, because acid solution can be clearly visible in sour pot, so still needing to for exhaust pipe to be inserted into sour pot
(identical as common process), then can be switched on chemical conversion, without standing.Chemical synthesis technology: with 10A electric discharge 1h, (as 50% is put
Electric depth), then with 3.6A (current density 5mA/mm2) constant-current charge is for 24 hours (charge volume 86.4Ah, 4.32C).
5) after second stage chemical conversion, after continuing charging 2 hours with 0.2A (corresponding to 0.01C) electric current, spent acid is taken out
It is shut down after to the greatest extent, is offline and finished battery can be obtained after product handling system.
Embodiment 2
6-DZM-20 battery semi-finished product are taken, acid adding and chemical conversion are carried out using the method for the present invention, sample making course is as follows:
1) first time acid adding, it is 1.10g/cm that density is added into acid lead batteries to be added3Sulfuric acid solution, acid adding volume
155ml (single lattice is saturated liquid absorption amount in 163~165ml, be saturation inhale acid amount 94% or so), using vacuum acid feeding mode into
Row, vacuum degree -0.06MPa, vacuum 1~2 time.
2) behind battery standing 1.5 hours completed first time acid adding, installation safety valve simultaneously opens first stage chemical conversion work
Skill, with 1.8A (current density 2.5mA/mm2) constant-current charge 38.9h (charge volume 70Ah, 3.5C).
3) after first stage chemical conversion, battery is subjected to second of acid adding, (vacuum is carried out using vacuum acid feeding mode
Degree -0.08MPa, vacuum 2~4 times), sour density is 1.58g/ml, and acid adding volume is 55ml.The determination and chemical conversion of battery acid adding amount
Total fluid loss and aggregate demand are related, need to be weighed to obtain dehydration data to the battery weight of each process when determining technique
Total acid adding volume and the acid adding volume in two stages are determined afterwards, and 6-DZM-20 is needed using the total acid adding volume of technology of the invention
Seeking Truth 210mL, therefore the acid adding volume of second stage is 210-155=55mL.
4) before second stage chemical conversion is opened, because acid solution can be clearly visible in sour pot, so still needing to for exhaust pipe to be inserted into sour pot
(identical as common process), then can be switched on chemical conversion, without standing.Chemical synthesis technology: with 10A electric discharge 1h, (as 50% is put
Electric depth), then with 5.5A (current density 7.5mA/mm2) constant-current charge 16.4h (charge volume 90Ah, 4.5C).
5) after second stage chemical conversion, after continuing charging 2 hours with 0.3A (corresponding to 0.015C) electric current, spent acid is taken out
It is shut down after to the greatest extent, is offline and finished battery can be obtained after product handling system.
Embodiment 3
6-DZM-20 battery semi-finished product are taken, acid adding and chemical conversion are carried out using the method for the present invention, sample making course is as follows:
1) first time acid adding, it is 1.20g/cm that density is added into acid lead batteries to be added3Sulfuric acid solution, acid adding volume
165ml (single lattice is saturated liquid absorption amount in 163~165ml, is that saturation inhales acid is measured 100% or so), using vacuum acid feeding mode
It carries out, vacuum degree -0.1MPa, vacuum 1~2 time.
2) behind battery standing 0.5 hour completed first time acid adding, installation safety valve simultaneously opens first stage chemical conversion work
Skill, with 3.6A (current density 5mA/mm2) constant-current charge 22.2h (charge volume 80Ah, 4.0C).
3) after first stage chemical conversion, battery is subjected to second of acid adding, (vacuum is carried out using vacuum acid feeding mode
Degree -0.08MPa, vacuum 2~4 times), sour density is 1.4g/ml, and acid adding volume is 45ml.The determination and chemical conversion of battery acid adding amount
Total fluid loss and aggregate demand are related, need to be weighed to obtain dehydration data to the battery weight of each process when determining technique
Total acid adding volume and the acid adding volume in two stages are determined afterwards, and 6-DZM-20 is needed using the total acid adding volume of technology of the invention
Seeking Truth 210mL, therefore the acid adding volume of second stage is 210-165=45mL.
4) before second stage chemical conversion is opened, because acid solution can be clearly visible in sour pot, so still needing to for exhaust pipe to be inserted into sour pot
(identical as common process), then can be switched on chemical conversion, without standing.Chemical synthesis technology: with 10A electric discharge 1.5h (as 75%
Depth of discharge), then with 3.6A (current density 5mA/mm2) constant-current charge is for 24 hours (charge volume 86.4Ah, 4.3C).
5) after second stage chemical conversion, after continuing charging 1.5 hours with 0.4A (corresponding to 0.02C) electric current, by spent acid
It is shut down after taking out to the greatest extent, is offline and finished battery can be obtained after product handling system.
Embodiment 4
6-DZM-20 battery semi-finished product are taken, acid adding and chemical conversion are carried out using the method for the present invention, sample making course is as follows:
1) first time acid adding, it is 1.25g/cm that density is added into acid lead batteries to be added3Sulfuric acid solution, acid adding volume
170ml (single lattice is saturated liquid absorption amount in 163~165ml, is that saturation inhales acid is measured 103% or so), using vacuum acid feeding mode
It carries out, vacuum degree -0.08MPa, vacuum 1~2 time.
2) behind battery standing 1 hour completed first time acid adding, installation safety valve simultaneously opens first stage chemical synthesis technology,
With 5.5A (current density 7.5mA/mm2) constant-current charge 16.4h (charge volume 90Ah, 4.5C).
3) after first stage chemical conversion, battery is subjected to second of acid adding, (vacuum is carried out using vacuum acid feeding mode
Degree -0.08MPa, vacuum 2~4 times), sour density is 1.25g/ml, and acid adding volume is 40ml.The determination and chemical conversion of battery acid adding amount
Total fluid loss and aggregate demand are related, need to be weighed to obtain dehydration data to the battery weight of each process when determining technique
Total acid adding volume and the acid adding volume in two stages are determined afterwards, and 6-DZM-20 is needed using the total acid adding volume of technology of the invention
Seeking Truth 210mL, therefore the acid adding volume of second stage is 210-170=40mL.
4) before second stage chemical conversion is opened, because acid solution can be clearly visible in sour pot, so still needing to for exhaust pipe to be inserted into sour pot
(identical as common process), then can be switched on chemical conversion, without standing.Chemical synthesis technology: with 10A electric discharge 0.5h (as 25%
Depth of discharge), then with 1.8A (current density 2.5mA/mm2) constant-current charge 38.9h (charge volume 70Ah, 3.5C).
5) after second stage chemical conversion, after continuing charging 2 hours with 0.2A (corresponding to 0.01C) electric current, spent acid is taken out
It is shut down after to the greatest extent, is offline and finished battery can be obtained after product handling system.
Comparative example 1
6-DZM-20 battery semi-finished product are taken, acid adding and chemical conversion are carried out using conventional production process, sample making course is as follows:
1) acid adding, it is 1.25g/cm that density is added into acid lead batteries to be added3Sulfuric acid solution, acid adding volume 225ml,
It is carried out using vacuum acid feeding mode, vacuum degree -0.08MPa, vacuum 3~4 times；
2) exhaust pipe is inserted into sour pot after the completion of acid adding, be switched on chemical conversion after standing 1 hour.Chemical synthesis technology: chemical conversion is total net
Charge volume 199.8Ah, total time 70h.It is specific as shown in table 1.
Table 1
| Step | Program | Electric current | Hour |
| 1 | Charging | 3 | 2 |
| 2 | Charging | 5 | 10 |
| 3 | Electric discharge | -7 | 1 |
| 4 | Charging | 5 | 5 |
| 5 | Electric discharge | -8 | 0.5 |
| 6 | Charging | 5 | 5 |
| 7 | Electric discharge | -8 | 1 |
| 8 | Charging | 5 | 4 |
| 9 | Electric discharge | -8 | 1 |
| 10 | Charging | 5 | 4 |
| 11 | Electric discharge | -10 | 1 |
| 12 | Charging | 5 | 4 |
| 13 | Electric discharge | -10 | 1.7 |
| 14 | Charging | 5 | 5 |
| 15 | Charging | 4.5 | 4 |
| 16 | Charging | 4 | 5.8 |
| 17 | Electric discharge | -10 | 2 |
| 18 | Charging | 5 | 5 |
| 19 | Charging | 3 | 4 |
| 20 | Charging | 2 | 2 |
| 21 | Charging | 0.3 | 2 |
3) final step of chemical synthesis technology shuts down after taking out spent acid to the greatest extent after 0.3A electric current charging 2 hours, is offline and pass through
Finished battery can be obtained after product handling system.
Embodiment 5
Case study on implementation 1~4 and the finished battery of comparative example 1 are dissected, and take out the same position of identical single lattice
Positive plate carries out after impregnating the acid solution washed away in pole plate, then is dried in vacuo, and pole plate sample is obtained.Then to pole plate sample into
Row XRD material phase analysis (8 °~90 ° of angle of diffraction, 4 °/min of scanning speed), sample position is identical to be tested, result such as table
Shown in 2.
Table 2
It is consistent that the data measured from XRD, which can be seen that Examples 1 to 4 and the conversion ratio of the active material of comparative example 1,
, formation effect is good.It can also find the α-PbO using the embodiment of the present invention 1~42Production quantity is substantially higher in comparative example,
α-PbO2Skeleton structure is acted as in positive active material, is the basis of battery long-life.α-PbO2Production quantity and formation process
It controls closely related, is created using the technology of the present invention conducive to α-PbO2The pH value of growth is neutral to subalkaline environment.
Embodiment 6
The finished battery of case study on implementation 1~4 and comparative example 1 is subjected to initial capacity and cycle life is tested, by 4/
Group is tested.
Cycle life test method:
1. electric discharge: 10A is discharged to 42V；
2. charging: constant pressure 59.2V current limliting 8A charges 5 hours；
It is as terminated 3. recycling and 1., being 2. lower than the 80% of rated capacity three times to capacity, this is not counted in cycle-index three times.
Test result is as shown in table 3.
Table 3
It can be seen that Examples 1 to 4 initial capacity from upper table data and be slightly below comparative example 1, but complied fully with standard and wanted
It asks.Cycle life is seen again, and comparative example is obviously better than using the cycle life of the Examples 1 to 4 of the technology of the present invention, promotes ratio
Example is up to 126% or more.
Embodiment 7
The technique used time and chemical conversion result of case study on implementation 1~4 and comparative example 1 are summarized in table 4.
Table 4
It can be seen that Examples 1 to 4 from upper table data and the conversion ratio of the active material of comparative example 1 be consistent, but change
It is always obviously fewer than comparative example 1 with the time at total net charge volume and chemical conversion, it is imitated that is to say, being illustrated using the chemical conversion of the technology of the present invention
Rate is obviously improved.
Claims (10)
1. a kind of long-life lead storage battery acid adding chemical synthesizing method, which comprises the following steps:
(1) first time acid adding, it is 1.05~1.25g/cm that density is added into acid lead batteries to be added3Low-gravity sulfuric acid solution,
It is that lead storage battery saturation inhales the 90%~105% of acid amount that volume, which is added,；
(2) first stage is melted into, charging, and charging total electricity is 3.5C~5.0C；
(3) second of acid adding, addition density are 1.25~1.65g/cm3High specific gravity sulfuric acid solution, fill it up with；
(4) second stage be melted into, first discharge and recharges afterwards, depth of discharge be 25%~80%, charging total electricity for 3.5C~
5.0C；
(5) spent acid is pumped.
2. long-life lead storage battery acid adding chemical synthesizing method as described in claim 1, which is characterized in that low-gravity in step (1)
The density of sulfuric acid solution is 1.10~1.20g/cm3。
3. long-life lead storage battery acid adding chemical synthesizing method as described in claim 1, which is characterized in that low-gravity in step (1)
The volume of sulfuric acid solution is that lead storage battery saturation inhales the 95%~100% of acid amount.
4. long-life lead storage battery acid adding chemical synthesizing method as described in claim 1, which is characterized in that high specific gravity in step (3)
The density of sulfuric acid solution is 1.35~1.50g/cm3。
5. long-life lead storage battery acid adding chemical synthesizing method as described in claim 1, which is characterized in that after the completion of acid adding chemical conversion,
The final densities for controlling electrolyte are 1.34~1.38g/cm3。
6. long-life lead storage battery acid adding chemical synthesizing method as described in claim 1, which is characterized in that taken out after second of acid adding true
2~4 times empty, vacuum degree is -0.06~-0.1MPa.
7. long-life lead storage battery acid adding chemical synthesizing method as described in claim 1, which is characterized in that pumped in step (5) remaining
Acid is taken out using electrification when sour, with electric current 0.01C~0.02C charging when acid is taken out in electrification.
8. long-life lead storage battery acid adding chemical synthesizing method as described in claim 1, which is characterized in that first stage chemical conversion and the
In two-stage chemical conversion, charging is all made of constant-current charge, current density 2.5mA/cm2~7.5mA/cm2。
9. long-life lead storage battery acid adding chemical synthesizing method as claimed in claim 8, which is characterized in that first stage chemical conversion and the
The density of charging current is 5mA/cm in two-stage chemical conversion2。
10. long-life lead storage battery acid adding chemical synthesizing method as described in claim 1, which is characterized in that quiet after first time acid adding
First stage chemical conversion is carried out again after setting 0.5~1.5h.
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