CN107317026A - The preparation method of four basic lead sulphates of lead-acid accumulator - Google Patents
The preparation method of four basic lead sulphates of lead-acid accumulator Download PDFInfo
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- CN107317026A CN107317026A CN201710364401.9A CN201710364401A CN107317026A CN 107317026 A CN107317026 A CN 107317026A CN 201710364401 A CN201710364401 A CN 201710364401A CN 107317026 A CN107317026 A CN 107317026A
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
- H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
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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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- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A kind of preparation method of four basic lead sulphates of lead-acid accumulator, (1) adds lead ball milling in the roller of ball mill, and collection obtains lead oxide powder；(2) lead oxide powder is dried 30 minutes in temperature is 350 DEG C 420 DEG C of drying machine, sends into incubator；Then weigh dried lead oxide powder 100kg to put into reactor immediately, add 20kg dilute sulfuric acids, and start agitator；(3) the dried lead oxide powder of 50kg and 10kg dilute sulfuric acids are put into toward continuation in reactor, reactor is warming up to 52 DEG C 55 DEG C, stirring stands 30 minutes after 20 minutes, then restarts stirring, stirs 10 minutes；(4) discharge valve of reactor is opened, it is injected in centrifugation apparatus, makes its solid-liquor separation using centrifugation apparatus；(5) waste water after separating is incorporated into wastewater collection bucket by water pump, and solid is in moist block white solid；(6) blocks of solid is inserted in drying baker and dried, then inserted pulverizer and grind, four basic lead sulphates are made.
Description
Technical field
The present invention relates to battery additive work technical field, and in particular to a kind of four basic lead sulphates of lead-acid accumulator
Preparation method.
Background technology
The solidification of lead acid battery positive electrode is a critical process of battery manufacture.The change of active material in the curing process
Learn and the architecture basics of physics are established, pole plate obtains mechanical strength, so that technological operation below can be carried out.According to
AOS is theoretical：With the progress of circulating battery, the neck region that positive active material is repeated between dilation, particle diminishes, made
The contact obtained between active material particle becomes more and more worse, and electric conductivity is deteriorated, and ultimately results in active material softening and shedding,
Battery capacity substantially decays, battery failure.Therefore improve active material charge acceptance and improve positive active material particle
Structure is to realize the key of battery long circulation life.
In lead-acid storage battery production, in order to extend battery cycle life, one of usual maximally effective measure is using height
The lead plaster of the basic lead sulphate of content four, can be obtained with the method for high temperature and cream or hot setting.Prepared with conventional method and cream
In have tribasic lead sulfate (abbreviation 3BS；3PbO·PbSO4·H2O), without the lead oxide and free lead reacted.Solidifying
Cheng Zhong, 3BS can further react four basic lead sulphates of generation (abbreviation 4BS under certain temperature damp condition with PbO；
4PbOPbSO4), free lead is further oxidized to lead oxide.
In the prior art, the general technology using high temperature and cream prepares 4BS, and lead powder, water, sulfuric acid solution and additive are entered
Row is mixed, and is made through physicochemical change with plasticity paste mixture.Thing phase composition with lead plaster after cream with it is added
Sulfuric acid amount and temperature during with cream it is closely related.Temperature and humidity is depended critically upon due to this reaction, in general industry
Under working condition, and cream temperature below 60 DEG C when, lead plaster mainly generates 3BS；Temperature is at 70 DEG C or so, and 4BS is big in lead plaster
Amount generation；When temperature is more than 80 DEG C, 4BS is mainly generated in lead plaster, but its crystalline size is about 5~100 μm, and size distribution
And its it is uneven, causing pole plate to be melted into, difficult, uniformity is poor, and battery initial capacity is low, and higher with cream temperature, 4BS's
Crystal grain is thicker.Therefore, in the prior art, substantially using with cream temperature at 80~90 DEG C, but size distribution and its
Uneven, causing pole plate to be melted into, difficult, uniformity is poor, and the low situation of battery initial capacity is serious, still unsatisfactory.
Therefore with cream acid adding before add be specifically manufactured 1~2% fine grained 4BS as 4BS crystal seeds, with cream and
It can greatly accelerate that 4BS is formed in subsequent solidification process, 4BS can also be formed comparatively fast when slightly lower temperature.In addition, thin
Particle 4BS addition can accelerate the oxidation of free lead in lead plaster.4BS application can be saved the time, save the energy and can be with
Accelerate equipment week then save the investment of equipment.
Existing comparative experimental research is confirmed, the quantity and crystal grain for the 4BS to be formed can be controlled as the 4BS of nucleus addition
Size, overcomes the problem of high content big crystal grain 4BS pole plates are melted into, the discharge performance of battery is excellent.Using the positive and negative of 4BS crystal seeds
Pole plate, due to its active material histological structure firmly, battery cycle life can increase.
At present, some 4BS additive products, such as Gu Li nations CuringBon (TM) Shandong Jin Keli electricity are had both at home and abroad
Source Science and Technology Ltd., the and for example SureCure (R) of Hammond companies, the TBLS+ (R) of Penox companies, AddiBatt (TM)
Addenda companies of the U.S..But the preparation method on 4BS has had not yet to see four alkali traditional in disclosed documents and materials, this area
The breakthrough of formula lead sulfate (4BS) pole plate manufacturing technology bottleneck nevertheless suffers from considerable restraint.
The content of the invention
The technical problems to be solved by the invention are to provide that a kind of method is relatively simple, the lead-acid accumulator of energy-conserving and environment-protective
With the preparation method of four basic lead sulphates.
The technical problems to be solved by the invention are realized using following technical scheme：
A kind of preparation method of four basic lead sulphates of lead-acid accumulator, specific method is as follows：
(1) lead is added in the roller of ball mill, one shower is installed in ball mill air inlet, dripped from shower
Water uniformly enter ball grinder interior with air inlet air intake, onto lead button, lead powder, reach the oxidizability and apparent density of lead powder
To requiring, collect and obtain lead oxide powder；
(2) lead oxide powder is dried 30 minutes in temperature is 350 DEG C -420 DEG C of drying machine, protected in feeding incubator
Temperature, then weighs dried lead oxide powder 100kg and puts into immediately in reactor, adds 20kg dilute sulfuric acids, and startup is stirred
Device is mixed, reaction 60 minutes is continuously stirred；
(3) the dried lead oxide powder of 50kg and 10kg dilute sulfuric acids are put into toward continuation in reactor, reactor is warming up to
52 DEG C -55 DEG C, stirring stands 30 minutes after 20 minutes, then restarts stirring, stirs 10 minutes, it is ensured that lead oxide powder is all thorough
Bottom is reacted, in slightly yellow milk, and then lifts and ensure the quality of generated finished product；
(4) discharge valve of reactor is opened, it is injected in centrifugation apparatus, makes its solid-liquor separation using centrifugation apparatus,
Liquid is really reacted waste water, and solid is then four basic lead sulphates；
(5) waste water after separating is incorporated into wastewater collection bucket by water pump, for preparing dilute sulfuric acid, the alkali formula sulphur of solid four
Lead plumbate is now in moist block white solid；
(6) the above-mentioned basic lead sulphate of blocks of solid four is inserted in drying baker and dried, then inserted in pulverizer, enter
Row is ground, and four basic lead sulphates are made.
The dilute sulfuric acid is in 25 DEG C of lower density 1.15-1.25g/ml.
In inwall injection reactor of the dilute sulfuric acid along reactor.
A kind of lead-acid battery anode diachylon added with above-mentioned four basic lead sulphate, it is by the group of following mass percent
Divide and be made：Lead powder 81%, pure water 9.5%, dilute sulfuric acid 7.5%, nano calcium oxide 0.1%, tin oxide 0.15%, Rare Earth Lanthanum
0.2%th, aquadag 0.35%, chopped fiber 0.5%, four basic lead sulphates 0.5%, potassium phosphate 0.2%.
Such as, 12Ah lead-acid accumulators plate railings of anode and cathode adds four alkali in the case of other process conditions do not become in lead plaster
Formula lead sulfate and it is not added with the pole plate that four basic lead sulphates make and is assembled into 12V-12Ah batteries carrying out contrast test：
12V-12Ah accumulator capacities are tested：
Volume test is that 6.0A constant-current discharges are electric to battery with 2 hour rates after lead accumulator full charge with national standard
Untill being pressed onto 10.5V.
Not plus the battery discharge times 132 minutes of four basic lead sulphates releases 13.2Ah capacitances；
Plus four the battery discharge time 155 minutes of basic lead sulphate release 15.5Ah capacitances.
Both compare relative capacity amount and improve 21%.
The test of 12V-12Ah accumulator cell charging and discharging cycle lives：
Battery uses current limliting constant-voltage charge to being discharged to 10.5V as a circulation using 2 hour rates i.e. 6.0A after 14.8V；
Not plus four basic lead sulphates accumulator cell charging and discharging cycle life be 286 times；
Plus four basic lead sulphate accumulator cell charging and discharging cycle life be 560 times；
More than 95% is improved with respect to charge and discharge circulation life.
The beneficial effects of the invention are as follows：Present invention process method is relatively simple, it is easy to produce in batches, while without discarded object
Produce, environmental pollution, crystal seed steady quality can will not be significantly improved accumulator property, improve active material
Utilization rate, so the capacity of lead-acid battery is greatly improved.
Brief description of the drawings
Fig. 1 is 4BS prepared by present invention XRD：
The prismatic figure for the 4BS samples that Fig. 2 is prepared for the present invention；
Graininess figure after the 4BS ball millings that Fig. 3 is prepared for the present invention.
Embodiment
In order that the technical means, the inventive features, the objects and the advantages of the present invention are easy to understand, tie below
Conjunction is specifically illustrating, and the present invention is expanded on further.
Embodiment 1
A kind of preparation method of four basic lead sulphates of lead-acid accumulator, specific method is as follows：
(1) lead is added in the roller of ball mill, one shower is installed in ball mill air inlet, dripped from shower
Water uniformly enter ball grinder interior with air inlet air intake, onto lead button, lead powder, reach the oxidizability and apparent density of lead powder
To requiring, collect and obtain lead oxide powder；
(2) lead oxide powder is dried 30 minutes in temperature is 380 DEG C of drying machine, be incubated in feeding incubator, then
Weigh dried lead oxide powder 100kg to put into reactor immediately, add 20kg dilute sulfuric acids, and start agitator, even
Continuous stirring reaction 60 minutes；
(3) the dried lead oxide powder of 50kg and 10kg dilute sulfuric acids are put into toward continuation in reactor, reactor is warming up to
53 DEG C, stirring stands 30 minutes after 20 minutes, then restarts stirring, stirs 10 minutes, it is ensured that lead oxide powder is all thoroughly anti-
Should, in slightly yellow milk, and then lift and ensure the quality of generated finished product；
(4) discharge valve of reactor is opened, it is injected in centrifugation apparatus, makes its solid-liquor separation using centrifugation apparatus,
Liquid is really reacted waste water, and solid is then four basic lead sulphates；
(5) waste water after separating is incorporated into wastewater collection bucket by water pump, for preparing dilute sulfuric acid, the alkali formula sulphur of solid four
Lead plumbate is now in moist block white solid；
(6) the above-mentioned basic lead sulphate of blocks of solid four is inserted in drying baker and dried, then inserted in pulverizer, enter
Row is ground, and four basic lead sulphates are made.
The dilute sulfuric acid is in 25 DEG C of lower density 1.15-1.25g/ml.
Embodiment 2
A kind of preparation method of four basic lead sulphates of lead-acid accumulator, specific method is as follows：
(1) lead is added in the roller of ball mill, one shower is installed in ball mill air inlet, dripped from shower
Water uniformly enter ball grinder interior with air inlet air intake, onto lead button, lead powder, reach the oxidizability and apparent density of lead powder
To requiring, collect and obtain lead oxide powder；
(2) lead oxide powder is dried 30 minutes in temperature is 420 DEG C of drying machine, be incubated in feeding incubator, then
Weigh dried lead oxide powder 100kg to put into reactor immediately, add 20kg dilute sulfuric acids, and start agitator, even
Continuous stirring reaction 60 minutes；
(3) the dried lead oxide powder of 50kg and 10kg dilute sulfuric acids are put into toward continuation in reactor, reactor is warming up to
55 DEG C, stirring stands 30 minutes after 20 minutes, then restarts stirring, stirs 10 minutes, it is ensured that lead oxide powder is all thoroughly anti-
Should, in slightly yellow milk, and then lift and ensure the quality of generated finished product；
(4) discharge valve of reactor is opened, it is injected in centrifugation apparatus, makes its solid-liquor separation using centrifugation apparatus,
Liquid is really reacted waste water, and solid is then four basic lead sulphates；
(5) waste water after separating is incorporated into wastewater collection bucket by water pump, for preparing dilute sulfuric acid, the alkali formula sulphur of solid four
Lead plumbate is now in moist block white solid；
(6) the above-mentioned basic lead sulphate of blocks of solid four is inserted in drying baker and dried, then inserted in pulverizer, enter
Row is ground, and four basic lead sulphates are made.
The dilute sulfuric acid is in 25 DEG C of lower density 1.15-1.25g/ml.
The 4BS products of this technique productions and the standard of production technology are as follows：
(1) raw materials for production are yellow lead (PbO) and H2SO4, process do not produce the three wastes；
(2) sample is tested through XRD, wherein not containing other impurity (Fig. 1)；
(3) in SEM photograph, the particle diameter of most particles is between 1~3 micron.
During actual judgement, the diffraction maximum of synthetic sample and 4BS standard PDF cards 23-333 diffraction maximum position complete one
Cause, but relative intensity is different.Reach that this is required, that is, judge sample as pure 4BS.If gained sample has unnecessary peak, sentence
It is set to the presence of impurity.
The particle diameter of the sample of synthesis can be determined from scanning electron microscope (SEM) photograph, laser particle analyzer can also be used to determine.This technique
The 4BS samples of synthesis are prismatic (such as Fig. 2), and sample length is 8~20 μm or so, and width is 1 μm or so.After ball milling
Sample is graininess, and particle diameter is less than 1 micron (such as Fig. 3)：Because as crystal seed, particle is the smaller the better.Therefore, every particle diameter is less than
It is qualified that 1~3 μm of person is considered as.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (5)
1. a kind of lead-acid accumulator preparation method of four basic lead sulphates, it is characterised in that specific method is as follows：
(1) lead is added in the roller of ball mill, one shower, the water dripped from shower is installed in ball mill air inlet
As air inlet air intake uniformly enters ball grinder interior, onto lead button, lead powder, reach the oxidizability and apparent density of lead powder and want
Ask, collection obtains lead oxide powder；
(2) lead oxide powder is dried 30 minutes in temperature is 350 DEG C -420 DEG C of drying machine, be incubated in feeding incubator, so
After weigh dried lead oxide powder 100kg and put into immediately in reactor, add 20kg dilute sulfuric acids, and start agitator,
Continuously stir reaction 60 minutes；
(3) toward continuing in reactor to put into the dried lead oxide powder of 50kg and 10kg dilute sulfuric acids, by reactor be warming up to 52 DEG C-
55 DEG C, stirring stands 30 minutes after 20 minutes, then restarts stirring, stirs 10 minutes, it is ensured that lead oxide powder is all thoroughly anti-
Should, in slightly yellow milk, and then lift and ensure the quality of generated finished product；
(4) discharge valve of reactor is opened, it is injected in centrifugation apparatus, makes its solid-liquor separation, liquid using centrifugation apparatus
Really reacted waste water, solid is then four basic lead sulphates；
(5) waste water after separating is incorporated into wastewater collection bucket by water pump, for preparing dilute sulfuric acid, the basic lead sulphate of solid four
Now in moist block white solid；
(6) the above-mentioned basic lead sulphate of blocks of solid four is inserted in drying baker and dried, then inserted in pulverizer, ground
Milling is broken, and four basic lead sulphates are made.
2. the lead-acid accumulator according to claim 1 preparation method of four basic lead sulphates, it is characterised in that described dilute
Sulfuric acid is in 25 DEG C of lower density 1.15-1.25g/ml.
3. the lead-acid accumulator according to claim 1 preparation method of four basic lead sulphates, it is characterised in that described dilute
In inwall injection reactor of the sulfuric acid along reactor.
4. the lead-acid accumulator according to claim 1 preparation method of four basic lead sulphates, it is characterised in that the step
Suddenly the temperature of drying machine is 380 DEG C in (2).
5. the lead-acid accumulator according to claim 1 preparation method of four basic lead sulphates, it is characterised in that the step
Suddenly the temperature of reactor is 53 DEG C in (3).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655105A (en) * | 2019-09-29 | 2020-01-07 | 巨江电源科技有限公司 | Preparation method of tetrabasic lead sulfate |
| CN113540441A (en) * | 2021-06-30 | 2021-10-22 | 双登集团股份有限公司 | Durable lead-acid storage battery positive lead paste and preparation method thereof |
| CN113880133A (en) * | 2021-09-23 | 2022-01-04 | 烟台金潮宇科蓄电池有限公司 | Preparation method of tetrabasic lead sulfate for lead-acid storage battery |
| CN114538503A (en) * | 2022-01-25 | 2022-05-27 | 超威电源集团有限公司 | Preparation method and device of high-purity tetrabasic lead sulfate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587141A (en) * | 2016-11-04 | 2017-04-26 | 浙江兜兰智能设备股份有限公司 | Production process and device for tetrabasic lead sulfate (4BS) |
-
2017
- 2017-05-22 CN CN201710364401.9A patent/CN107317026A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587141A (en) * | 2016-11-04 | 2017-04-26 | 浙江兜兰智能设备股份有限公司 | Production process and device for tetrabasic lead sulfate (4BS) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655105A (en) * | 2019-09-29 | 2020-01-07 | 巨江电源科技有限公司 | Preparation method of tetrabasic lead sulfate |
| CN110655105B (en) * | 2019-09-29 | 2022-04-05 | 巨江电源科技有限公司 | Preparation method of tetrabasic lead sulfate |
| CN113540441A (en) * | 2021-06-30 | 2021-10-22 | 双登集团股份有限公司 | Durable lead-acid storage battery positive lead paste and preparation method thereof |
| CN113880133A (en) * | 2021-09-23 | 2022-01-04 | 烟台金潮宇科蓄电池有限公司 | Preparation method of tetrabasic lead sulfate for lead-acid storage battery |
| CN114538503A (en) * | 2022-01-25 | 2022-05-27 | 超威电源集团有限公司 | Preparation method and device of high-purity tetrabasic lead sulfate |
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Application publication date: 20171103 |