CN104167569B - The method extending 2V fixed pattern analysing valve control type lead-acid accumulator battery cycle life - Google Patents
The method extending 2V fixed pattern analysing valve control type lead-acid accumulator battery cycle life Download PDFInfo
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- CN104167569B CN104167569B CN201410374031.3A CN201410374031A CN104167569B CN 104167569 B CN104167569 B CN 104167569B CN 201410374031 A CN201410374031 A CN 201410374031A CN 104167569 B CN104167569 B CN 104167569B
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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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- 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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- 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
A kind of method extending 2V fixed pattern analysing valve control type lead-acid accumulator battery cycle life, including being dried with cream, coated plate, solidification, assemble and the operation such as chemical conversion, plate coating process will be coated on the grid that weight is identical respectively with the positive and negative lead plaster of system, the cream amount that is coated with of anode plate grid is 1.33 1.43 times that negative electrode grid is coated with cream amount, and the painting cream amount of anode plate grid is according to 1.70g/cm2‑1.74g/cm2Control；In electrolyte used by formation process, Ludox is Ludox with the mass ratio of sulfuric acid solution: sulfuric acid solution=1:10.6 10.9, sulfuric acid solution concentration is 34 35%.The present invention is directed to affect the principal element of battery life, existing 2V fixed pattern VRLA lead-acid accumulator processing technology is improved, test shows, the 2V fixed pattern VRLA lead-acid accumulator deeper cavity life-span of battery compared with the battery that current technology produces using the inventive method to make can improve three or four times.
Description
Technical field
The present invention relates to a kind of storage battery production method, especially a kind of 2V fixed pattern VRLA that extends stores
The method of battery cycle life, belongs to battery technology field.
Background technology
Valve controlled sealed lead-acid accumulator is also known as VRLA accumulator, and it is born in 20 century 70s, due to
VRLA is hermetic, will not leak acid, and will not have as old-fashioned lead-acid accumulator when discharge and recharge
Acid mist is released and etching apparatus, pollutes environment, so enjoying great popularity, being widely used.2V fixed pattern VRLA
Lead-acid accumulator is a kind of accumulator being mainly used in communication base station, back-up source and power system, this storage
Being mainly characterized by the case of condition of power supply is bad of battery can be discharged the long period, meets electrical equipment
Demand.The projected life of 2V fixed pattern VRLA lead-acid accumulator up to 10-15, and in actual use
Battery life normally only between 3-5, the even less than 2 years batteries having cannot normal power supply, cause money
The significant wastage in source.Additionally, the shelf-life of usual accumulator is to determine according to the projected life of battery, because of
Substantial amounts of the returning to of this short life accumulator causes the biggest economic loss to enterprise.In the face of above-mentioned situation, prolong
Long 2V fixed pattern VRLA cycle life of lead-acid accumulator be improve the performance of enterprises, reduce the wasting of resources urgently solve
Problem certainly
Summary of the invention
It is an object of the invention to provide a kind of 2V fixed pattern analysing valve control type lead-acid accumulator battery cycle life of extending
Method, use the method the cycle life of fixed pattern VRLA cycle life of lead-acid accumulator can improve three-
Four times.
Problem of the present invention realizes with following technical proposals:
A kind of method extending 2V fixed pattern analysing valve control type lead-acid accumulator battery cycle life, including with cream, coated plate,
Solidification is dried, assembles and the operation such as chemical conversion, will be coated in respectively with the positive and negative lead plaster of system in described plate coating process
On the grid that weight is identical, the cream amount that is coated with of anode plate grid is 1.33-1.43 times that negative electrode grid is coated with cream amount, wherein
The painting cream amount of anode plate grid is according to 1.70g/cm2-1.74g/cm2Control；Electrolyte used by described formation process
Middle Ludox is Ludox with the mass ratio of sulfuric acid solution: sulfuric acid solution=1:10.6-10.9, described sulphuric acid
Solution concentration is 34-35%.
The method of above-mentioned prolongation 2V fixed pattern analysing valve control type lead-acid accumulator battery cycle life, will in described assembly process
Dividing plate and the positive/negative plate being dried through overcuring load in cell jar, the spacing between positive plate, negative plate
For 1.5-1.6 millimeter.
The method of above-mentioned prolongation 2V fixed pattern analysing valve control type lead-acid accumulator battery cycle life, filling of described formation process
Electric process is carried out in the following manner:
First stage: electric current (A) 60, time (h) 4；
Second stage: electric current (A) 75, time (h) 14；
Phase III: electric current (A)-70, time (h) 1；
Fourth stage: electric current (A) 80, time (h) 10；
5th stage: electric current (A) 60, the time (h) 10；
6th stage: electric current (A)-60, the time (h) 3；
7th stage: electric current (A) 80, the time (h) 5；
8th stage: electric current (A) 60, the time (h) 15；
9th stage: electric current (A)-30, the time (h) 3；
Tenth stage: electric current (A) 60, the time (h) 10.
The failure mode of end-of-life battery through further investigation and is analyzed by the present invention, it is believed that cause 2V solid
The sizing short main cause of VRLA cycle life of lead-acid accumulator is: 1, positive material(PAM) softening；2, the later stage
Battery charge acceptance is poor, 3, the internal resistance of cell increase.For above three affect battery life main because of
Element, is improved the concerned process steps of existing fixed pattern VRLA lead-acid accumulator processing technology: by suitably
Improve positive active material content and reduce the positive discharge degree of depth, delay positive pole softening rate；By reducing electricity
Solve liquid-tight degree and improve the Lead oxide brown forming densification when charging modes makes accumulator charge at positive pole, reducing electricity
The electrode potential in pond, improves the charge acceptance of battery；Subtract by reducing the distance between positive/negative plate
Baby battery internal resistance.Test shows, use the inventive method make 2V fixed pattern VRLA lead-acid accumulator with
The deeper cavity life-span of battery compared by the battery that current technology produces can improve three-four times, and this achievement is to improve
Utilization rate and the minimizing environmental pollution of resource have a significant effect, and improve battery and use the cycle, significantly drop
Low return to the tremendous economic loss that battery causes to enterprise.
Detailed description of the invention
By the failure mode analysis (FMA) of end-of-life battery being drawn 2V fixed pattern VRLA waste lead-acid accumulators
Main former as follows: 1, positive material(PAM) softening (active substance loosen)；2, the charging of later stage battery
By ability；3, the internal resistance of cell increases.The main cause causing battery positive electrode active material to soften is lead sulfate
The structure of layer and depth of discharge, and the structure of sulphuric acid lead layer depends on its dissolubility in sulphuric acid and diffusion
Situation.The passivation of dissolubility the highest then lead electrode is the slowest, and lead sulfate crystallization is the biggest, and sulphuric acid lead layer is the thickest, when
The least by the density of sulphuric acid lead layer during same electricity, sulphuric acid lead layer affects the real area of Lead oxide brown.
When the sulphuric acid lead layer formed closely time, will form that real surface area is little and close titanium dioxide lead layer.And
The Lead oxide brown with less real surface area must have the most stronger surface texture layer.This
The positive active material of spline structure must have longer service life.Therefore want to delay positive pole to lose efficacy, a side
Face density of electrolyte to be reduced forms it into the titanium dioxide lead layer of densification, and on the other hand positive pole to be properly increased is lived
Property content of material, reduce the positive discharge degree of depth to delay positive pole softening rate.The present invention will in plate coating process
It is coated in respectively on the grid that weight is identical with the positive and negative lead plaster of system according to normal process, the painting cream of anode plate grid
Amount is negative electrode grid painting 1.33-1.43 times of cream amount, wherein the painting cream amount of anode plate grid according to
1.70g/cm2-1.74g/cm2Control.Positive plate is coated with cream amount and improves 22-25% compared to existing technology by this improvement,
Negative plate is coated with cream amount and improves 16-18% compared to existing technology, in particular improves positive plate opposing negative polarity plate
It is coated with the ratio (the cream amount that is coated with of prior art anode plate grid is about negative electrode grid and is coated with 1.27 times of cream amount) of cream amount,
So as to slowing down positive material(PAM) softening process, extend the life-span of positive plate.
In the electrolyte that the present invention is used in formation process, Ludox is that silicon is molten with the mass ratio of sulfuric acid solution
Glue: sulfuric acid solution=1:10.6-10.9, (Ludox in prior art: sulfuric acid solution is about 1:11.5)
Sulfuric acid solution concentration is 34-35%.The density of electrolyte is reduced by adding the Ludox of larger proportion, low
The Lead oxide brown of densification is formed at positive pole, it is also possible to reduce battery when density of electrolyte can make accumulator charge
Electrode potential, improve battery charge acceptance.But Ludox ratio is crossed conference and is caused electrolysis liquid-tight
Degree reduces, and affects the discharge capacity of battery.The present invention, based on great number tested data, determines 2V fixed pattern VRLA
Lead-acid accumulator Ludox controls at Ludox with the ratio of sulfuric acid solution: sulfuric acid solution=1:10.55-10.9.
The charging process of formation process of the present invention is carried out in the following manner:
This charging process can effectively control the temperature in formation process, keeps the temperature between 40-58 DEG C, from
And ensure the positive pole preferable Lead oxide brown of uniform generating structure.Battery temperature in charging process can rise,
If the too high meeting of temperature causes electrolyte skewness, affect positive pole and generate uniform Lead oxide brown structure, for
Prevent temperature in battery forming process too high, use smaller current charging in 1,5,8 stages of charging process.
10th stage used smaller current to be too high in order to prevent battery charging from terminating rear internal temperature, caused interior external pressure
Power is excessive, deforms after causing housing cooling.
Affect the principal element that the internal resistance of cell increases and have the distance between the positive and negative plate of electrolyte content and battery, and
VRLA lead-acid accumulator uses lean solution to be closely assembled structure, along with increasing of battery access times, the dehydration of battery
Amount is also increasing, and owing to the electrolyte of VRLA lead-acid accumulator is adsorbed in dividing plate, the dehydration of battery can cause
Dividing plate dries up, and the minimizing of moisture in electrolyte can cause electrolyte flow to be deteriorated, so that the internal resistance of cell increases
Greatly.Increase the solution of the content of Ludox, beneficially the problems referred to above in the electrolytic solution.Additionally from formula R=ρ L/S
(in formula R be resistance, ρ be resistivity, L be the length of conductor, the distance of i.e. two interpolars, S are conductor
Sectional area) in, it can be seen that reduce distance L of positive and negative interpolar, the internal resistance of cell can be reduced.Along with positive pole
Spacing between plate, negative plate reduces, and the thickness of dividing plate can reduce accordingly accordingly, and thinning dividing plate rear bulkhead
Also can be increased by the probability of negative plate sulphuric acid penetration of lead dendritic crystal, it is therefore desirable to the spacing of positive/negative plate is controlled one
Individual rational scope.Spacing between positive plate, negative plate is controlled at 1.5-1.6 millimeter (relatively by the present invention
Prior art reduces 20-25%), show according to result of the test, above-mentioned spacing is for 2V fixed pattern VRLA lead
Acid accumulator is suitable.
The specific embodiment of several present invention presented below:
Example 1: use existing technique and make positive and negative lead plaster, take the grid of identical weight, each positive grid according to
1.74g/cm2Painting cream amount coat anode diachylon, each negative grid is according to 1.308g/cm2Painting cream amount coat negative pole
Lead plaster, then carries out solidification and is dried；Take 20 positive plates, 21 negative plates, 1.12 × 2mm thickness
Dividing plate welds poling group, loads in the cell jar of length × width × height=236 × 168 × 312, positive plate,
Spacing between negative plate is 1.5 millimeters, uses groove lid and terminal sealing glue sealed cell；Add 5883g
The H of 34.4%2SO4Solution and 555g Ludox, do after then carrying out formation charging by following formation charging mode
Become resultant battery.
| Stage | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Electric current A | 60 | 75 | -70 | 80 | 60 | -60 | 80 | 60 | -30 | 60 |
| Time h | 4 | 14 | 1 | 10 | 10 | 3 | 5 | 15 | 3 | 10 |
Example 2: use existing technique and make positive and negative lead plaster, take the grid of identical weight, each positive grid according to
1.713g/cm2Painting cream amount coat anode diachylon, each negative grid is according to 1.215g/cm2Painting cream amount coat negative
Lead plaster, then carries out solidification and is dried；Take 20 positive plates, 21 negative plates, 1.12 × 2mm thickness
Dividing plate welds poling group, loads in the cell jar of length × width × height=236 × 168 × 312, positive plate,
Spacing between negative plate is 1.55 millimeters, uses groove lid and terminal sealing glue sealed cell, adds 5950g
The H of 34%2SO4Solution and 550g Ludox, do after then carrying out formation charging by following formation charging mode
Become resultant battery.
| Stage | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Electric current A | 60 | 75 | -70 | 80 | 60 | -60 | 80 | 60 | -30 | 60 |
| Time h | 4 | 14 | 1 | 10 | 10 | 3 | 5 | 15 | 3 | 10 |
Example 3: use existing technique and make positive and negative lead plaster, take the grid of identical weight, each positive grid according to
1.70g/cm2The painting cream amount of g coats anode diachylon, and each negative grid is according to 1.23g/cm2Painting cream amount coat negative pole
Lead plaster, then carries out solidification and is dried；Take 20 positive plates, 21 negative plates, 1.12 × 2mm thickness
Dividing plate welds poling group, loads in the cell jar of length × width × height=236 × 168 × 312, positive plate,
Spacing between negative plate is 1.6 millimeters, uses groove lid and terminal sealing glue sealed cell, adds 5951g 35%
H2SO4Solution and 546g Ludox, be made to after then carrying out formation charging by following formation charging mode
Product battery.
| Stage | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Electric current A | 60 | 75 | -70 | 80 | 60 | -60 | 80 | 60 | -30 | 60 |
| Time h | 4 | 14 | 1 | 10 | 10 | 3 | 5 | 15 | 3 | 10 |
Following table is the 2V fixed pattern VRLA lead-acid accumulator produced according to above-described embodiment and produces according to prior art
2V fixed pattern VRLA lead-acid accumulator (comparative example) 100%DOD cycle life correction data is (with 2V 500Ah
As a example by battery)
By data in table it can be seen that use the 2V fixed pattern VRLA lead-acid accumulator that the inventive method makes
The cycle life of battery is substantially increased compared with the same specification accumulator that current technology produces.
Claims (3)
1. the method extending 2V fixed pattern analysing valve control type lead-acid accumulator battery cycle life, including with cream, coated plate,
Solidification is dried, assembles and formation process, it is characterized in that, by the positive and negative lead plaster with system in described plate coating process
Being coated in respectively on the grid that weight is identical, wherein, the cream amount that is coated with of anode plate grid is that negative electrode grid is coated with cream amount
1.33-1.43 times, the painting cream amount of anode plate grid is according to 1.70g/cm2-1.74g/cm2Control；
In electrolyte used by described formation process, Ludox is Ludox with the mass ratio of sulfuric acid solution: sulphuric acid
Solution=1:10.6-10.9, described sulfuric acid solution concentration is 34-35%.
The side of prolongation 2V fixed pattern analysing valve control type lead-acid accumulator battery cycle life the most according to claim 1
Method, is characterized in that, in described assembly process, dividing plate and the positive/negative plate being dried through overcuring is loaded accumulator
In groove, the spacing between positive plate, negative plate is 1.5-1.6 millimeter.
The side of prolongation 2V fixed pattern analysing valve control type lead-acid accumulator battery cycle life the most according to claim 2
Method, is characterized in that, the charging process of described formation process is carried out in the following manner:
First stage: electric current 60A, time 4h；
Second stage: electric current 75A, time 14h；
Phase III: electric current-70A, time 1h；
Fourth stage: electric current 80A, time 10h；
5th stage: electric current 60A, time 10h；
6th stage: electric current-60A, time 3h；
7th stage: electric current 80A, time 5h；
8th stage: electric current 60A, time 15h；
9th stage: electric current-30A, time 3h；
Tenth stage: electric current 60A, time 10h.
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| CN201410374031.3A CN104167569B (en) | 2014-08-01 | 2014-08-01 | The method extending 2V fixed pattern analysing valve control type lead-acid accumulator battery cycle life |
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| CN201410374031.3A CN104167569B (en) | 2014-08-01 | 2014-08-01 | The method extending 2V fixed pattern analysing valve control type lead-acid accumulator battery cycle life |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1848508A (en) * | 2005-04-13 | 2006-10-18 | 北京天中树科技发展有限公司 | Nano lead-acid accumulator battery |
| CN102306799A (en) * | 2010-03-24 | 2012-01-04 | 衡阳瑞达电源有限公司 | Deep cycle-resistant lead-acid storage battery plate and manufacturing method |
| CN103515580A (en) * | 2013-10-23 | 2014-01-15 | 漳州市华威电源科技有限公司 | Processing technique of lead-acid green plate batteries |
| CN103762388A (en) * | 2014-01-17 | 2014-04-30 | 黄山振龙电源有限公司 | Formation technology of valve control lead-acid storage battery for electric vehicle |
-
2014
- 2014-08-01 CN CN201410374031.3A patent/CN104167569B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1848508A (en) * | 2005-04-13 | 2006-10-18 | 北京天中树科技发展有限公司 | Nano lead-acid accumulator battery |
| CN102306799A (en) * | 2010-03-24 | 2012-01-04 | 衡阳瑞达电源有限公司 | Deep cycle-resistant lead-acid storage battery plate and manufacturing method |
| CN103515580A (en) * | 2013-10-23 | 2014-01-15 | 漳州市华威电源科技有限公司 | Processing technique of lead-acid green plate batteries |
| CN103762388A (en) * | 2014-01-17 | 2014-04-30 | 黄山振龙电源有限公司 | Formation technology of valve control lead-acid storage battery for electric vehicle |
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