CN103943832B - A kind of applicable energy storage lead acid accumulator polar plate solidification technique - Google Patents
A kind of applicable energy storage lead acid accumulator polar plate solidification technique Download PDFInfo
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- CN103943832B CN103943832B CN201410111986.XA CN201410111986A CN103943832B CN 103943832 B CN103943832 B CN 103943832B CN 201410111986 A CN201410111986 A CN 201410111986A CN 103943832 B CN103943832 B CN 103943832B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
- H01M4/21—Drying of pasted electrodes
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- 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
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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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Abstract
The present invention relates to a kind of applicable energy storage lead acid accumulator polar plate solidification technique, described curing process comprises moisturizing stage, heat preservation solidification stage and drying stage; The steam containing hydrogen peroxide is passed in the moisturizing stage; The steam containing ozone is passed in the heat preservation solidification stage.By curing process of the present invention, manufacture pole plate, be assembled into battery, the resistance to cycle life of battery significantly improves, battery initial capacity is than not occurring difference because of hot setting, dive to fill and deeply put, overcharge shallow superposition cycle life of putting more than 1600 times, there is not argillization phenomenon in polar board surface, is the desirable curing mode of energy-storage battery.
Description
Technical field
The present invention relates to storage battery field, be specifically related to a kind of applicable energy storage lead acid accumulator polar plate solidification technique improving lead acid accumulator useful life.
Background technology
Lead-acid battery (Lead-acidbattery) electrode is made primarily of plumbous and oxide, and electrolyte is a kind of storage battery of sulfuric acid solution.From Frenchman Pulan spy (G.Plante) in invention lead acid accumulator in 1859, experienced by the development course of nearly 150 years, lead acid accumulator is in theoretical research, significant progress is obtained in product category and kind, product electric property etc., no matter be in traffic, communication, electric power, military affairs or in navigation, each economic field of aviation, lead acid accumulator all serves indispensable important function.In recent years, along with the acceleration of urbanization and the expansion of city scope, the magnitude of traffic flow increases severely.Although the development of the vehicles such as automobile rapidly, be subject to using the impact of the factors such as the relatively costly and rise of the oil price of price, make electric bicycle with its advantage such as spry and light, convenient, cheap, city's field depth is subject to the welcome of consumers in general at home.Lead acid accumulator is because cost performance is high, power characteristic is good, and self discharge is little, low price, application of having got back in electric bicycle in recent years.
Lead acid accumulator is internalized into from simplifying operating procedure step and energy efficient, the angle of emissions reduction is worthy to be popularized, and formulates rational container formation production technology, is the key carrying out container formation.Be internalized into lead-acid storage battery production Manufacturing Technology Development so far, its chemical synthesis technology still continues to use traditional multistage direct current formation regime so far mostly, Battery formation efficiency is low, production cycle is long, Ye You minority producer adopts pulse technique, namely positive negative pulse stuffing or intermittent pulse change into, but are not promoted so far.For being internalized into lead acid accumulator, due to the characteristic of lead-calcium alloy, for ensureing its cycle life, packaging technology will ensure absolute tight assembling, causes the pole plate of inside battery thus, that sour saturation inhaled by dividing plate is all relatively low, change under this lean solution state, internal resistance is higher, is unfavorable for the diffusion of electrolyte and temperature, and Battery formation difficulty is large, efficiency is low, it is long to change into the cycle, and high-voltage charge changes into the corrosion exacerbating grid for a long time, shorten the useful life of battery.
At present, according to Chinese Ministry of Environmental Protection to lead acid accumulator industry requirement, be internalized into the direction that processing storage battery mode is following industry.Energy storage lead acid accumulator is mainly used in garden lamp, the illumination of street lamp lamp.Battery cycle life is mostly at about 300 times, and energy storage lead acid accumulator user uses just to be needed to change for about 1 year.As battery polar plate solidification mode and solidification effect, very big to the performance impact of storage battery.Adopt bad curing mode, the early stage capacitance loss of pole plate PCL(will be brought).Very large technology barrier is brought to the new forms of energy market demand.
China Patent Publication No. CN101459258A, publication date on June 17th, 2009, name is called internal chemical synthetic reverse charging chemical process for lead acid battery, this application case discloses a kind of internal chemical synthetic reverse charging chemical process for lead acid battery, comprise the acid filling of lead acid accumulator or encapsulating step and charge step, after acid filling or encapsulating step complete and before charge step, reverse charging is carried out to battery.Its weak point is, although the method can improve the conductivity between grid and active material, circulating battery is low for useful life.
Summary of the invention
The object of the invention is to fail in early days to solve existing lead acid accumulator, the defect that useful life is lower and carry out charge and discharge cycles under providing one to be adapted at various ambient temperature, the applicable energy storage lead acid accumulator polar plate solidification technique that battery cycle life is high.
To achieve these goals, the present invention is by the following technical solutions:
A kind of applicable energy storage lead acid accumulator polar plate solidification technique, described curing process comprises moisturizing stage, heat preservation solidification stage and drying stage; The steam containing hydrogen peroxide is passed in the moisturizing stage; Pass into containing steam ozoniferous in the heat preservation solidification stage.
As preferably, the moisturizing stage comprises the following steps: 1) temperature 40-45 DEG C, relative humidity 100%, curing time 10h;
2) temperature 50-55 DEG C, relative humidity 100%, curing time 6h, passing into containing mass fraction is the steam of 0.05%-0.09% hydrogen peroxide;
3) temperature 60-65 DEG C, relative humidity 98%, curing time 8h, passing into containing mass fraction is the steam of 0.05%-0.09% hydrogen peroxide.In the technical program, what this stage adopted is interim raising curing temperature, and relative humidity controls at 98-100%, and the object of the program is fully contacted with lead plaster by pole plate moisture, make between grid and lead plaster, to form stable network configuration, very crucial effect is played to the intensity of pole plate; Pass into the object of the steam containing hydrogen peroxide, one is to keep humidity, and two is in order to accelerated oxidation.
As preferably, the heat preservation solidification stage comprises the following steps: 1) under the environment of relative humidity 95%, static 4h;
2) temperature 50-55 DEG C, relative humidity 90%, curing time 5h, passing into containing mass fraction is 0.1%-0.5% steam ozoniferous;
3) temperature 50-55 DEG C, relative humidity 80%, curing time 5h, passing into containing mass fraction is 0.1%-0.5% steam ozoniferous;
4) temperature 50-55 DEG C, relative humidity 70%, curing time 8h, passing into containing mass fraction is 0.1%-0.5% steam ozoniferous;
5) temperature 60-65 DEG C, relative humidity 50%, curing time 8h.
In the technical program, this stage adopts metastable temperature to be cured pole plate, but relative humidity reduces gradually, to make in pole plate ozone in lead plaster and air fully oxidized, this stage is that free lead declines the fastest stage, the inner free lead content of pole plate drops to approximate 2-5% from 15%, form firmly corrosion layer between lead plaster and grid, there is the intensity of high-quality, from one meter of height, freely falling body drops in ground grading, and the lead plaster that comes off accounts for pole plate weight≤1%; Because of pole plate lead plaster, that oxidation reaction occurs between 70-90% is the fastest, and improving temperature can accelerated reaction process; Pass into the object containing steam ozoniferous, one is to keep humidity, and two is the oxygen that ozone provides needed for reflection, in order to accelerate the oxidation of lead plaster, and stops in step 5) that to pass into be to allow humidity remain on 50%.
As preferably, drying stage temperature 75-80 DEG C, relative humidity 0%, curing time 15h.In the technical program, this temperature makes pole plate dry in the short period of time, and temperature is low, and can extend drying time, temperature is too high, and because pole plate lead plaster main component is that burning is plumbous, the impact of being expanded with heat and contract with cold, pole plate easily occurs crackle when going out curing room.
As preferably, pole plate is before entering curing room, and require that the watering of solidification flooring is moistening, solidify indoor temperature control 40-45 DEG C, relative humidity controls >=95%.
As preferably, pole plate after coated plate, before entering curing room, rest on outdoor time≤15min, positive lead plaster moisture control is at >=100g/kg lead plaster, and negative lead plaster moisture control is at >=90g/kg lead plaster.
As preferably, anode diachylon apparent density controls at 4.20-4.35g/ml, and cathode lead plaster apparent density controls at 4.30-4.45g/ml.
As preferably, solidify rear positive plate lead paste free lead content≤2.5%, negative plate lead plaster free lead content≤4%.
As preferably, steam intake is 1.2-1.5L/h.
The invention has the beneficial effects as follows by curing process of the present invention, manufacture pole plate, be assembled into battery, the resistance to cycle life of battery significantly improves, battery initial capacity is than not occurring difference because of hot setting, dive to fill and deeply put, overcharge shallow superposition cycle life of putting more than 1600 times, there is not argillization phenomenon in polar board surface, is the desirable curing mode of energy-storage battery.
Accompanying drawing explanation
Fig. 1 is lead acid accumulator circulation discharge curve prepared by the embodiment of the present invention 1.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just in order to further illustrate the features and advantages of the present invention, instead of limiting to the claimed invention.
Embodiment 1
A kind of applicable energy storage lead acid accumulator polar plate solidification technique, described curing process comprises moisturizing stage, heat preservation solidification stage and drying stage;
The moisturizing stage comprises the following steps: 1) temperature 40 DEG C, relative humidity 100%, curing time 10h;
2) temperature 50 C, relative humidity 100%, curing time 6h, passing into containing mass fraction is the steam of 0.05% hydrogen peroxide;
3) temperature 60 C, relative humidity 98%, curing time 8h, passing into containing mass fraction is the steam of 0.07 hydrogen peroxide;
The heat preservation solidification stage comprises the following steps:
1) under the environment of relative humidity 95%, static 4h;
2) temperature 50 C, relative humidity 90%, curing time 5h, passing into containing mass fraction is 0.1% steam ozoniferous;
3) temperature 50 C, relative humidity 80%, curing time 5h, passing into containing mass fraction is 0.2% steam ozoniferous;
4) temperature 50 C, relative humidity 70%, curing time 8h, passing into containing mass fraction is 0.1% steam ozoniferous;
5) temperature 60 C, relative humidity 50%, curing time 8h;
Drying stage temperature 75 DEG C, relative humidity 0%, curing time 15h.Wherein, steam intake is 1.2L/h.
Pole plate is before entering curing room, and require that the watering of solidification flooring is moistening, solidification indoor temperature controls 40 DEG C, and relative humidity controls >=95%; Pole plate after coated plate, before entering curing room, rest on outdoor time≤15min, positive lead plaster moisture control is at >=100g/kg lead plaster, and negative lead plaster moisture control is at >=90g/kg lead plaster; Anode diachylon apparent density controls at 4.20g/ml, and cathode lead plaster apparent density controls at 4.30g/ml; Positive plate lead paste free lead content≤2.5% after solidification, negative plate lead plaster free lead content≤4%.
Embodiment 2
A kind of applicable energy storage lead acid accumulator polar plate solidification technique, described curing process comprises moisturizing stage, heat preservation solidification stage and drying stage;
The moisturizing stage comprises the following steps: 1) temperature 43 DEG C, relative humidity 100%, curing time 10h;
2) temperature 52 DEG C, relative humidity 100%, curing time 6h, passing into containing mass fraction is the steam of 0.07% hydrogen peroxide;
3) temperature 63 DEG C, relative humidity 98%, curing time 8h, passing into containing mass fraction is the steam of 0.08% hydrogen peroxide.
The heat preservation solidification stage comprises the following steps:
1) under the environment of relative humidity 95%, static 4h;
2) temperature 51 DEG C, relative humidity 90%, curing time 5h, passing into containing mass fraction is 0.2% steam ozoniferous;
3) temperature 52 DEG C, relative humidity 80%, curing time 5h, passing into containing mass fraction is 0.5% steam ozoniferous;
4) temperature 53 DEG C, relative humidity 70%, curing time 8h, passing into containing mass fraction is 0.5% steam ozoniferous;
5) temperature 62 DEG C, relative humidity 50%, curing time 8h;
Drying stage temperature 78 DEG C, relative humidity 0%, curing time 15h.Wherein, steam intake is 1.3L/h.
Pole plate is before entering curing room, and require that the watering of solidification flooring is moistening, solidification indoor temperature controls 45 DEG C, and relative humidity controls >=95%; Pole plate after coated plate, before entering curing room, rest on outdoor time≤15min, positive lead plaster moisture control is at >=100g/kg lead plaster, and negative lead plaster moisture control is at >=90g/kg lead plaster; Anode diachylon apparent density controls at 4.30g/ml, and cathode lead plaster apparent density controls at 4.35g/ml; Positive plate lead paste free lead content≤2.5% after solidification, negative plate lead plaster free lead content≤4%.
Embodiment 3
A kind of applicable energy storage lead acid accumulator polar plate solidification technique, described curing process comprises moisturizing stage, heat preservation solidification stage and drying stage;
The moisturizing stage comprises the following steps: 1) temperature 45 C, relative humidity 100%, curing time 10h;
2) temperature 55 DEG C, relative humidity 100%, curing time 6h, passing into containing mass fraction is the steam of 0.09% hydrogen peroxide;
3) temperature 65 DEG C, relative humidity 98%, curing time 8h, passing into containing mass fraction is the steam of 0.09% hydrogen peroxide.
The heat preservation solidification stage comprises the following steps:
1) under the environment of relative humidity 95%, static 4h;
2) temperature 55 DEG C, relative humidity 90%, curing time 5h, passing into containing mass fraction is 0.5% steam ozoniferous;
3) temperature 55 DEG C, relative humidity 80%, curing time 5h, passing into containing mass fraction is 0.4% steam ozoniferous;
4) temperature 55 DEG C, relative humidity 70%, curing time 8h, passing into containing mass fraction is 0.4% steam ozoniferous;
5) temperature 65 DEG C, relative humidity 50%, curing time 8h;
Drying stage temperature 80 DEG C, relative humidity 0%, curing time 15h.Wherein, steam intake is 1.5L/h.
Pole plate is before entering curing room, and require that the watering of solidification flooring is moistening, solidification indoor temperature controls 45 DEG C, and relative humidity controls >=95%; Pole plate after coated plate, before entering curing room, rest on outdoor time≤15min, positive lead plaster moisture control is at >=100g/kg lead plaster, and negative lead plaster moisture control is at >=90g/kg lead plaster; Anode diachylon apparent density controls at 4.35g/ml, and cathode lead plaster apparent density controls at 4.45g/ml; Positive plate lead paste free lead content≤2.5% after solidification, negative plate lead plaster free lead content≤4%.
Embodiment 1 is prepared pole plate, is assembled into lead acid accumulator and carries out cyclic discharge capacity test, the results are shown in Figure 1.As seen from Figure 1, the present invention is by above-mentioned curing process, manufacture battery, the resistance to cycle life of battery significantly improves, battery initial capacity is sufficient, dive to fill and deeply put, overcharge shallow superposition cycle life of putting more than 1600 times, spending in vain or argillization phenomenon does not appear in polar board surface, is the desirable curing mode of energy-storage battery.
Claims (7)
1. an applicable energy storage lead acid accumulator polar plate solidification technique, it is characterized in that, described curing process comprises moisturizing stage, heat preservation solidification stage and drying stage; The steam containing hydrogen peroxide is passed in the moisturizing stage; The steam containing ozone is passed in the heat preservation solidification stage; The moisturizing stage comprises the following steps:
1) temperature 40-45 DEG C, relative humidity 100%, curing time 10h;
2) temperature 50-55 DEG C, relative humidity 100%, curing time 6h, passing into containing mass fraction is the steam of 0.05%-0.09% hydrogen peroxide;
3) temperature 60-65 DEG C, relative humidity 98%, curing time 8h, passing into containing mass fraction is the steam of 0.05%-0.09% hydrogen peroxide;
The heat preservation solidification stage comprises the following steps:
1) under the environment of relative humidity 95%, static 4h;
2) temperature 50-55 DEG C, relative humidity 90%, curing time 5h, passing into containing mass fraction is the steam of 0.1%-0.5% ozone;
3) temperature 50-55 DEG C, relative humidity 80%, curing time 5h, passing into containing mass fraction is the steam of 0.1%-0.5% ozone;
4) temperature 50-55 DEG C, relative humidity 70%, curing time 8h, passing into containing mass fraction is the steam of 0.1%-0.5% ozone;
5) temperature 60-65 DEG C, relative humidity 50%, curing time 8h.
2. one according to claim 1 is applicable to energy storage lead acid accumulator polar plate solidification technique, it is characterized in that, drying stage temperature 75-80 DEG C, relative humidity 0%, curing time 15h.
3. one according to claim 1 is applicable to energy storage lead acid accumulator polar plate solidification technique, it is characterized in that, pole plate, before entering curing room, requires that the watering of solidification flooring is moistening, solidification indoor temperature control 40-45 DEG C, relative humidity controls >=95%.
4. one according to claim 1 is applicable to energy storage lead acid accumulator polar plate solidification technique, it is characterized in that, pole plate is after coated plate, before entering curing room, rest on outdoor time≤15min, positive lead plaster moisture control is at >=100g/kg lead plaster, and negative lead plaster moisture control is at >=90g/kg lead plaster.
5. one according to claim 1 is applicable to energy storage lead acid accumulator polar plate solidification technique, and it is characterized in that, anode diachylon apparent density controls at 4.20-4.35g/mL, and cathode lead plaster apparent density controls at 4.30-4.45g/mL.
6. one according to claim 1 is applicable to energy storage lead acid accumulator polar plate solidification technique, it is characterized in that, positive plate lead paste free lead content≤2.5% after solidification, negative plate lead plaster free lead content≤4%.
7. one according to claim 1 is applicable to energy storage lead acid accumulator polar plate solidification technique, it is characterized in that, it is 1.2-1.5L/h that steam passes into speed.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104600255B (en) * | 2014-12-30 | 2017-01-04 | 浙江天能动力能源有限公司 | A kind of curing process of polar plate of lead acid storage battery |
| CN105261731B (en) * | 2015-09-06 | 2018-04-06 | 山东超威电源有限公司 | A kind of curing and dying process of anode plate for lead acid accumulator |
| CN105428605B (en) * | 2015-12-03 | 2018-06-29 | 超威电源有限公司 | The technique that a kind of lead-acid battery negative pole plate reduces hardening time |
| CN105552364B (en) * | 2016-01-07 | 2017-12-29 | 超威电源有限公司 | A kind of lead acid battery positive electrode exempts to solidify the preparation method of lead plaster |
| CN108232123B (en) * | 2017-12-26 | 2020-05-12 | 浙江天能动力能源有限公司 | Curing process for positive plate of lead-acid storage battery for electric automobile |
| CN108711610B (en) * | 2018-04-20 | 2020-09-01 | 天能电池集团股份有限公司 | Lead storage battery pole plate curing and drying process |
| CN109698324B (en) * | 2018-06-01 | 2021-08-31 | 骆驼集团蓄电池研究院有限公司 | Curing and drying process of green plate for lead-acid battery |
| CN109065846B (en) * | 2018-07-28 | 2020-09-22 | 河南超威电源有限公司 | Process for curing positive electrode plate of lead-acid storage battery |
| CN109742330B (en) * | 2019-01-31 | 2021-09-10 | 安徽超威电源有限公司 | Two-day high-temperature curing process for power lead-acid storage battery |
| CN109873124A (en) * | 2019-01-31 | 2019-06-11 | 安徽超威电源有限公司 | A kind of power lead-acid storage battery high temperature curing process |
| CN112582586B (en) * | 2020-11-13 | 2022-03-22 | 骆驼集团蓄电池研究院有限公司 | Preparation process of lead-acid battery suitable for high-temperature use |
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