CN101707249A - Storage battery anode lead plaster capable of enhancing SAE standard high temperature service life and preparation method - Google Patents
Storage battery anode lead plaster capable of enhancing SAE standard high temperature service life and preparation method Download PDFInfo
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- CN101707249A CN101707249A CN200910175251A CN200910175251A CN101707249A CN 101707249 A CN101707249 A CN 101707249A CN 200910175251 A CN200910175251 A CN 200910175251A CN 200910175251 A CN200910175251 A CN 200910175251A CN 101707249 A CN101707249 A CN 101707249A
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- 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
Abstract
The invention discloses a storage battery anode lead plaster capable of enhancing SAE standard high temperature service life and a preparation method, aiming at solving the problem of high temperature service life of lead-acid storage batteries. The technical scheme is that the lead plaster raw materials are prepared by the following substances in parts by weight: 100 of lead powder, 0.05-0.1 of fiber, 0.1-1.0 of superfine barium sulfate, 0.05-0.2 of carbon black, and 0.1-0.4 of magnesium sulfate. The invention selects superfine barium sulfate as anode additive, thus delaying contraction and rigidification of anode plate under high temperature and prolonging service life of the storage battery; magnesium sulfate and carbon black improve the porosity of the anode active substance, facilitates dispersion of sulfuric acid and is beneficial for starting performance of the storage battery. Proved by test data, main technical performance index can perfectly achieve and surpass the standard requirement, and satisfy the requirement of the automobile on the high temperature service life of the storage battery.
Description
Technical field
The present invention relates to a kind of lead-acid accumulator anode diachylon and preparation method, particularly can improve the accumulator anode diachylon of SAE standard high temperature service life, belong to the battery technology field.
Background technology
Positive/negative plate is the parts of storage battery most critical, and the quality of positive/negative plate has directly determined the discharge capacity of storage battery and recycled the life-span.Along with the develop rapidly of auto industry, more and more higher to the performance requirement of lead acid accumulator, one of them is exactly that storage battery was had higher requirement in the useful life under the hot conditions.Basic lead sulphate in the anode diachylon, lead oxide, lead sulfate etc. are oxidized to PbO in formation process
2The microporosity aggregation, and hand over mutually and form a continuous integral body.Under the normal condition, it is basicly stable that the cellular structure of positive active material can keep, and can stand thousands of times charge and discharge cycles.But in different ambient temperature and discharging and recharging under the system, different failure modes can appear in storage battery, in case and the structure of active material is badly damaged, discharge process just is difficult to proceed.Under the normal temperature condition, along with charge and discharge cycles, positive active material PbO
2Particle can diminish gradually, lose connection between particle gradually, the active material aperture becomes big, and positive discharge decreased performance, macro manifestations are the active material argillization.And under hot conditions, positive active material is in higher-energy state, the active material reduced volume obviously strengthens with the trend that reduces energy, shrink process is accelerated in charge and discharge process, show as positive active material caking, sclerosis, the final active material sulfation that takes place, the pole plate overall structure is destroyed when serious.After the sclerosis, the active material porosity reduces, and has blocked sour passage, and electric conductivity reduces, and causes the battery discharging performance to reduce, and the life-span ends.
When at present general lead acid accumulator was produced, the anode diachylon prescription was: lead powder, fiber, dilute sulfuric acid and water.As automobile start lead acid accumulator with high temperature service life requirement, the development test that must further be correlated with, break through traditional manufacturing technique, in the hope of improving the lead acid accumulator high temperature service life, guarantee SAE standard life requirements (SAE under the hot conditions, Society ofAutomotive Engineers, what the SAE standard was meant that U.S. automotive engineer learns storage battery sub-committee of electric equipment committee issue is applicable to that 12v, idle capacity were smaller or equal to 180 minutes automotive battery standard).
Summary of the invention
Technical problem to be solved by this invention provides a kind of accumulator anode diachylon and preparation method of the SAE of raising standard high temperature service life, thereby makes lead acid accumulator still have good cycle life under hot conditions.
The alleged problem of the present invention is solved by following technical scheme:
A kind of accumulator anode diachylon that improves the SAE standard high temperature service life, its special feature is: described lead plaster raw material is made by following weight unit's matter: lead powder 100, fiber 0.05～0.1, ultra-fine barium sulfate 0.1～1.0, carbon black 0.05～0.2, magnesium sulfate 0.1～0.4.
The above-mentioned accumulator anode diachylon that improves the SAE standard high temperature service life, the particle diameter of described ultra-fine barium sulfate is less than 30 microns; Described carbon black is a conductive black.
The above-mentioned accumulator anode diachylon that improves the SAE standard high temperature service life, PbO content is 70-85% in the described lead powder.
A kind of preparation method who improves the accumulator anode diachylon of SAE standard high temperature service life, it is undertaken by following operation:
A. prepare burden: take by weighing each solid material by above-mentioned lead plaster raw material proportioning;
B. do to mix: with above-mentioned lead plaster solid material put into paste mixing machine dried be mixed even;
C. wet mixing: take by weighing the pure water of raw material lead powder weight 10～12%, the magnesium sulfate of proportional quantity is added in this pure water, fully join together in the paste mixing machine after the dissolving, stir;
D. drench acid: add the 1.400g/cm that lead powder weight 4～8%, density are in the spray mode while stirring
3Sulfuric acid solution and the cream temperature below 65 ℃, go out the cream temperature and be lower than 45 ℃.
The present invention breaks through traditional lead-acid accumulator anode diachylon technology of preparing, select interpolation ultra-fine barium sulfate, carbon black, magnesium sulfate to join in the anode diachylon active material, the solution positive active material charges and discharge contraction, the sclerosis problem in the circulation electric process under hot conditions, effectively improve the electricity of positive active material and lead and porosity, prolonged the SAE high-temperature cycle life of positive plate.Test data shows, adopt the lead acid accumulator of the technology of the present invention manufacturing to compare with general maintenance-free lead accumulator, have suitable cold-starting ability and charging and accept performance, heavy-current discharge after the every unit of its high temperature service life finishes and general prescription battery comparison with voltage are higher, obtained longer high temperature service life, its basic mechanical design feature index can meet and exceed SAE standard (seeing Table 1) fully, satisfies the requirement of automobile to the lead acid accumulator high temperature service life.
Description of drawings
Fig. 1 is the positive plate active material SEM figure of barium sulfate-containing of the present invention;
Fig. 2 is conventional art positive plate SEM figure.
Embodiment
Anode diachylon of the present invention aims at automobile start and designs with storage battery, the anode additive that it adopts, its suitable ratio is ultra-fine barium sulfate 0.1%～1.0%, magnesium sulfate 0.1%～0.4%, carbon black 0.05%～0.2%, and core technology is to add ultra-fine barium sulfate and strict control adding proportion.Traditional theory is thought BaSO
4Definitely anode diachylon can not be sneaked into, otherwise the softening and shedding of positive active material can be quickened and end-of-life in advance.Reason is that the positive plate life-span failure mode under the normal temperature condition is a softening and shedding, and if introducing BaSO
4As PbSO
4The nucleus of particle can crystal grain thinning, and the easier active material that causes is softening.And by discovering, the battery that uses under hot environment, its positive active material have the trend of particle increase, sulfation, and the anode failure mode of using down with normal temperature is opposite.Think BaSO
4The crystal grain thinning effect particle that can delay positive active material increase and sulfation inorganic additive BaSO
4Under anodal high potential, can not lose efficacy because of decomposition.The adding proportion of described ultra-fine barium sulfate must strictly be controlled, and the too high obstruction positive active material of content conductivity influences the life-span; Too low then not the having of content slowed down the effect that positive active material shrinks, and positive plate can shrink sclerosis fast, and battery cycle life reduces.
Described ultra-fine barium sulfate guarantees that particle diameter less than 30 microns, has the characteristic of high dispersion.Barium sulfate has the lattice parameter approximate with lead sulfate, and high degree of dispersion as the nucleus of crystal of lead sulfate, need not to form the lead sulfate nucleus during discharge in active material, so just can not produce to form the necessary degree of supersaturation of nucleus.The lead sulfate that generates under the low condition of degree of supersaturation is more loose porous, helps the diffusion of sulfuric acid.Barium sulfate also makes the discharging product lead sulfate of positive active material separate out on barium sulfate, makes active material be unlikely to the sulfuric acid lead layer covers, and can react with sulfuric acid more swimmingly.In charging process, because barium sulfate is inertia, do not participate in the redox reaction of electrode, high degree of dispersion is in active material, brown lead oxide and brown lead oxide or brown lead oxide and lead sulfate are mechanically separated, be difficult for intergranular merging takes place, can play the effect that prevents that the positive active material specific area is shunk under the high temperature, the sclerosis, the piece that have effectively delayed positive active material take off, and have prolonged the SAE high temperature service life of storage battery.
The adding of magnesium sulfate has improved the porosity of positive active material.Magnesium sulfate can dissolve in sulfuric acid solution, thereby stays micropore in active material, has improved the porosity of active material, helps sulfuric acid electrolyte and is diffused into pole plate inside, satisfies the reaction of the inner active material of pole plate.The introducing of carbon black has improved the conductivity of positive plate, promotes the even formation and the distribution of active material in the formation process, and active material reaction in use is more even; The diffusion that the tiny micropore of the oxidized formation of carbon black promotes acid solution of carrying out along with circulation helps charge and discharge cycles.
Referring to Fig. 1, Fig. 2, contrasting two figure, can to find out that Fig. 1 adds the positive active material crystal grain that positive plate forms after the barium sulfate relatively finer and smoother, and Fig. 2 the positive plate positive active material crystal grain of barium sulfate-containing is not thick relatively.As seen the anode diachylon prescription adds the effect that can obviously play crystal grain thinning behind the barium sulfate, and this can play corresponding effect for slowing down positive active material contraction under the hot conditions, sclerosis, sulfation.
Table 1 is the technical indicator that the lead acid accumulator of employing anode diachylon making of the present invention reaches through test:
Table 1
By table 1 data as can be seen, the maintenance-free lead-acid storage battery for starting that adopts the present invention to make has suitable cold-starting ability and charging to accept performance with general maintenance-free lead accumulator, heavy-current discharge and conventional formulation battery comparison with voltage after the every unit of high temperature service life finishes are higher, have obtained longer high temperature service life.
Several instantiations below are provided:
Embodiment 1: with 100kg PbO content is that 70%～85% lead powder adds in the paste mixing machine, add fiber, the 0.05kg carbon black of 0.05kg, the ultra-fine barium sulfate of 0.1kg simultaneously, above-mentioned material is stirred, add 10kg then and be dissolved with purifying waste water of 0.1kg magnesium sulfate, after hygrometric state mixed, drenching density fast was 1.400g/cm
3Control and cream temperature be less than 65 ℃ in the sulfuric acid solution 4kg of (25 ℃) and the cream process, reaction evenly and temperature drop to below 45 ℃, can go out the cream use.
Embodiment 2: with 100kgPbO content is that 70%～85% lead powder adds in the paste mixing machine, add fiber, the 0.1kg carbon black of 0.07kg, the ultra-fine barium sulfate of 0.5kg simultaneously, above-mentioned material is stirred, add 11kg then and be dissolved with purifying waste water of 0.2kg magnesium sulfate, after hygrometric state mixed, drenching density fast was 1.400g/cm
3Control and cream temperature be less than 65 ℃ in the sulfuric acid solution 6kg of (25 ℃) and the cream process, reaction evenly and temperature drop to below 45 ℃, can go out the cream use.
Embodiment 3: with 100kg PbO content is that 70%～85% lead powder adds in the paste mixing machine, add fiber, the 0.2kg carbon black of 0.1kg, the ultra-fine barium sulfate of 0.8kg simultaneously, above-mentioned material is stirred, add 12kg then and be dissolved with purifying waste water of 0.4kg magnesium sulfate, after hygrometric state mixed, drenching density fast was 1.400g/cm
3Control and cream temperature be less than 65 ℃ in the sulfuric acid solution 8kg of (25 ℃) and the cream process, reaction evenly and temperature drop to below 45 ℃, can go out the cream use.
Embodiment 4: with 100kg PbO content is that 70%～85% lead powder adds in the paste mixing machine, add fiber, the 0.12kg carbon black of 0.06kg, the ultra-fine barium sulfate of 1.0kg simultaneously, above-mentioned material is stirred, add 12kg then and be dissolved with purifying waste water of 0.3kg magnesium sulfate, after hygrometric state mixed, drenching density fast was 1.400g/cm
3Control and cream temperature be less than 65 ℃ in the sulfuric acid solution 8kg of (25 ℃) and the cream process, reaction evenly and temperature drop to below 45 ℃, can go out the cream use.
The anode diachylon of preparation as stated above is coated on the grid, solidifies 24h through 40 ℃, 98%RH, produce and just give birth to plate through 70 ℃, the dry 24h of 20%RH again, the negative plate of giving birth to can adopt automobile start battery terminal negative lead plaster and the manufacturing of pole plate manufacture craft.Through pole plate change into, dry, divide plate after, use PE pocket type dividing plate, the private casing of packing into, sealing becomes the automobile start maintenance-free battery.
Claims (4)
1. accumulator anode diachylon that can improve the SAE standard high temperature service life, it is characterized in that: described lead plaster raw material is made by following weight unit's matter: lead powder 100, fiber 0.05～0.1, ultra-fine barium sulfate 0.1～1.0, carbon black 0.05～0.2, magnesium sulfate 0.1～0.4.
2. the accumulator anode diachylon that improves the SAE standard high temperature service life according to claim 1 is characterized in that: the particle diameter of described ultra-fine barium sulfate is less than 30 microns; Described carbon black is a conductive black.
3. the accumulator anode diachylon that improves the SAE standard high temperature service life according to claim 2 is characterized in that: PbO content is 70-85% in the described lead powder.
4. method for preparing as the accumulator anode diachylon of claim 1 or the 2 or 3 described SAE of raising standard high temperature service lifes is characterized in that it is undertaken by following operation:
A. prepare burden: take by weighing each solid material by above-mentioned lead plaster raw material proportioning;
B. do to mix: with above-mentioned lead plaster solid material put into paste mixing machine dried be mixed even;
C. wet mixing: take by weighing the pure water of raw material lead powder weight 10～12%, the magnesium sulfate of material proportional quantity is added in this pure water, fully join together in the paste mixing machine after the dissolving, stir;
D. drench acid: add the 1.400g/cm that raw material lead powder weight 4～8%, density are in the spray mode while stirring
3Sulfuric acid solution and the cream temperature below 65 ℃, go out the cream temperature and be lower than 45 ℃.
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|---|---|---|---|
| CN200910175251A CN101707249A (en) | 2009-11-26 | 2009-11-26 | Storage battery anode lead plaster capable of enhancing SAE standard high temperature service life and preparation method |
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| CN200910175251A CN101707249A (en) | 2009-11-26 | 2009-11-26 | Storage battery anode lead plaster capable of enhancing SAE standard high temperature service life and preparation method |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102074696A (en) * | 2010-12-29 | 2011-05-25 | 风帆股份有限公司 | Vacuum preparation method for positive pole lead paste of lead-acid storage battery |
| CN102163719A (en) * | 2011-03-23 | 2011-08-24 | 浙江振龙电源股份有限公司 | Formula and manufacturing method of lead plaster for lead-acid battery positive plate |
| CN102891295A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Method for preparing carbon-based composite material of super lead acid storage battery |
| CN105280916A (en) * | 2015-02-11 | 2016-01-27 | 济源市万洋绿色能源有限公司 | Composite paste for inner formation of lead-acid storage battery |
| CN106099116A (en) * | 2016-08-25 | 2016-11-09 | 四川荣联电子科技有限公司 | Additive for lead-acid accumulator anode diachylon |
| CN106252609A (en) * | 2016-08-25 | 2016-12-21 | 四川荣联电子科技有限公司 | Slow down the lead-acid accumulator anode diachylon that positive active material comes off |
| CN107732338A (en) * | 2016-10-27 | 2018-02-23 | 杨春晓 | The method for improving or extending lead-acid accumulator or battery pack service life |
| CN110854448A (en) * | 2019-11-29 | 2020-02-28 | 湖南科舰能源发展有限公司 | AGM storage battery for starting and stopping automobile and preparation method thereof |
| CN111261846A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Lead-carbon battery positive electrode and preparation and application thereof |
| CN111600018A (en) * | 2019-10-23 | 2020-08-28 | 骆驼集团蓄电池研究院有限公司 | Negative lead paste suitable for high-temperature and low-temperature environments, lead-acid storage battery and preparation method |
-
2009
- 2009-11-26 CN CN200910175251A patent/CN101707249A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102074696B (en) * | 2010-12-29 | 2013-10-16 | 风帆股份有限公司 | Vacuum preparation method for positive pole lead paste of lead-acid storage battery |
| CN102074696A (en) * | 2010-12-29 | 2011-05-25 | 风帆股份有限公司 | Vacuum preparation method for positive pole lead paste of lead-acid storage battery |
| CN102163719A (en) * | 2011-03-23 | 2011-08-24 | 浙江振龙电源股份有限公司 | Formula and manufacturing method of lead plaster for lead-acid battery positive plate |
| CN102163719B (en) * | 2011-03-23 | 2013-08-07 | 浙江振龙电源股份有限公司 | Formula and manufacturing method of lead plaster for lead-acid battery positive plate |
| CN102891295A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Method for preparing carbon-based composite material of super lead acid storage battery |
| CN105280916B (en) * | 2015-02-11 | 2017-12-19 | 济源市万洋绿色能源有限公司 | Lead-acid accumulator is internalized into conjunction cream |
| CN105280916A (en) * | 2015-02-11 | 2016-01-27 | 济源市万洋绿色能源有限公司 | Composite paste for inner formation of lead-acid storage battery |
| CN106099116A (en) * | 2016-08-25 | 2016-11-09 | 四川荣联电子科技有限公司 | Additive for lead-acid accumulator anode diachylon |
| CN106252609A (en) * | 2016-08-25 | 2016-12-21 | 四川荣联电子科技有限公司 | Slow down the lead-acid accumulator anode diachylon that positive active material comes off |
| CN107732338A (en) * | 2016-10-27 | 2018-02-23 | 杨春晓 | The method for improving or extending lead-acid accumulator or battery pack service life |
| CN111261846A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Lead-carbon battery positive electrode and preparation and application thereof |
| CN111600018A (en) * | 2019-10-23 | 2020-08-28 | 骆驼集团蓄电池研究院有限公司 | Negative lead paste suitable for high-temperature and low-temperature environments, lead-acid storage battery and preparation method |
| CN110854448A (en) * | 2019-11-29 | 2020-02-28 | 湖南科舰能源发展有限公司 | AGM storage battery for starting and stopping automobile and preparation method thereof |
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Application publication date: 20100512 |