CN1404165A - Microcapsule for valve-controlled sealed lead-acid storage battery and preparation method thereof - Google Patents
Microcapsule for valve-controlled sealed lead-acid storage battery and preparation method thereof Download PDFInfo
- Publication number
- CN1404165A CN1404165A CN02112896A CN02112896A CN1404165A CN 1404165 A CN1404165 A CN 1404165A CN 02112896 A CN02112896 A CN 02112896A CN 02112896 A CN02112896 A CN 02112896A CN 1404165 A CN1404165 A CN 1404165A
- Authority
- CN
- China
- Prior art keywords
- capsule
- micro
- battery
- preparation
- spray drying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003094 microcapsule Substances 0.000 title claims abstract description 29
- 239000002253 acid Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001694 spray drying Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000002775 capsule Substances 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000013268 sustained release Methods 0.000 claims description 5
- 239000012730 sustained-release form Substances 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- 206010011732 Cyst Diseases 0.000 claims description 4
- 208000031513 cyst Diseases 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 2
- 238000005192 partition Methods 0.000 claims description 2
- 238000005191 phase separation Methods 0.000 claims description 2
- -1 poly-carbon ester Chemical class 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 238000007667 floating Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract 3
- 239000007787 solid Substances 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 206010011906 Death Diseases 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007762 w/o emulsion Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000027790 Rib fracture Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002224 dissection Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Secondary Cells (AREA)
Abstract
A micro capsule for valve-controlled sealed lead-acid accumulator and its preparing method, characterized in that the capsule wall is solid porous shell made of high molecular material, the capsule is packed with deionized water or sulfuric acid electrolyte; the preparation method generally adopts a spray drying method. The microcapsule prepared by the invention is filled in partial gaps or all gaps in the battery, on one hand, the deformation growth of a polar plate can be prevented, and on the other hand, the water loss of the battery in the use process can be supplemented, so that the service life of the lead-acid storage battery is greatly prolonged, wherein the floating charge service life is prolonged by about 60 percent, and the cycle life is prolonged by about 80 percent.
Description
Technical field
The present invention relates to a kind of micro capsule for valve controlled sealed lead-acid accumulator and preparation method thereof, belong to the sealed lead acid storage battery technical field.
Background technology
Lead-acid battery relies on its good ratio of performance to price, occupies critical role in the secondary cell field.In the power supply system of all aqueous solution, lead-acid battery has higher operating voltage, heavy-current discharge performance and high low temperature performance preferably, and it both had been suitable for the floating charge use, also be suitable for simultaneously starting and recycling, so lead-acid battery is widely used in fields such as stand-by power supply, energy reserve and electrical source of power.
Although the valve controlled sealed lead-acid accumulator technology is increasingly mature, also there are many problems in the VRLA battery.Valve controlled sealed lead-acid accumulator in use often because dehydration causes dry the inefficacy, has shortened the useful life of storage battery greatly.Analyze its main cause and be because the decomposition of water, oxygen of separating out and hydrogen increase inner pressure of battery, start vent valve gas is discharged outside the battery container, take water and sulfuric acid simultaneously out of, cause battery dehydration, capacity to descend until end-of-life.Another major reason that causes lead-acid battery to lose efficacy is the distortion of pole plate in charge and discharge process, and the result of distortion makes the linear increase of grid size, even indivedual rib fracture, causes mechanical short circuit easily, and final entire cell is damaged.
Summary of the invention
The objective of the invention is to overcome weak point of the prior art, provide a kind of distortion growth that prevents pole plate and battery dehydration in use dry, thereby improve the battery micro capsule for valve controlled sealed lead-acid accumulator in useful life, and and then provide the preparation method of this micro-capsule.
Technical scheme of the present invention is: palace gate control formula sealed lead acid storage battery is the porous solid phase housing that macromolecular material constitutes with the cyst wall of micro-capsule, is surrounded by sustained release liquid in the capsule.
Above-mentioned micro-capsule forms almost spherical outward, and diameter is 10～1000um.Macromolecular material is any in the poly-carbon ester of stable existence in strong acid media, polymethyl methacrylate, polyacrylic resin, poly hydroxy ethyl acrylate, the paracyanogen base alkyl acrylate.Sustained release liquid is the deionized water of resistivity greater than 5M Ω cm, or density is less than or equal to 1.3g/cm
3The analytical pure sulfuric acid aqueous solution.
Technical scheme of the present invention also comprises the preparation method of described micro-capsule, and this method comprises in spray drying process, emulsion phase separation method, condensed phase partition method, the water encystation method in the dispersion and water.
Described spray drying process is that described macromolecular material is dissolved in the dichloroethanes solvent, solution concentration is 4～6%, then sulfuric acid is added under stirring state, forms emulsion, again this emulsion is sprayed in the spray drying tower of 30～40 ℃ of thermal currents, and then make micro-capsule.
The micro-capsule that adopts technical solution of the present invention to make is filled in part space or all gaps of valve controlled sealed lead-acid accumulator inside, irritating the acid front and back for battery all is suitable for, slowed down the distortion of the dry and pole plate of electrolyte in the battery, so useful life of having improved battery greatly, float life has improved about 60%, cycle life has improved about 80%, this greatly the market competitiveness of valve controlled sealed lead-acid accumulator.
Embodiment
Be cyst material below with the polymethyl methacrylate, adopt spray drying method for preparation to be surrounded by the micro-capsule of sulfuric acid electrolyte.
Polymethyl methacrylate is dissolved in the dichloroethanes solvent, and the concentration of solution is about 5%, then with 1.05g/cm
3Sulfuric acid under condition of stirring, add, form water in oil emulsion, this water in oil emulsion is sprayed in the spray drying tower that thermal current (35 ℃) are arranged, form water in oil droplet, oil phase is the polymethyl methacrylate that is dissolved in the dichloroethanes, and water is an aqueous sulfuric acid.Dichloroethanes volatilizees with thermal current, reclaims separately.Polymethyl methacrylate is frozen into the porous solid phase housing, constitutes the micro-capsule that is surrounded by sulfuric acid electrolyte.The temperature and the flow velocity of air-flow in the composition of oil phase and the drying tower depended in the porosity of micro-capsule and aperture.The concentration of polymethyl methacrylate is low more, and then the cyst wall of micro-capsule is thin more, and porosity and aperture are big more; The temperature of air-flow and flow velocity are high more in the drying tower, and the porosity of micro-capsule and aperture are big more.
To be filled in all gaps of two 2V300Ah batteries and two 12V10Ah batteries with the micro-capsule that is surrounded by sulfuric acid electrolyte of method for preparing respectively.Wherein, the 2V300Ah battery carries out the test of high temperature float life, and the 12V10Ah battery carries out cycling life test, carries out blank contrast test simultaneously, and the test device therefor is the charge-discharge test instrument of U.S. Arbin company.The high temperature float life be in 60 ℃ environment with 2.23V to the continuous floating charge of battery 1 month, in 25 ℃ environment, battery is carried out 10 hour rate capacity check then, constitute a cycling element like this, when battery 10 hour rate capacity drop to 80%, battery end of life.Industry---the sealing lead acid storage battery for electric vehicle standard is carried out with reference to People's Republic of China's machinery in cycling life test, in 25 ℃ environment, with 5A current discharge 1.4h, then with 1.5A charging 5.6h, constitute a cycling element like this, as discharge 1.4h, accumulator voltage is continuous when being lower than 9.6V 3 times, and cycle life stops.Result of the test is as shown in Table 1 and Table 2:
Table 1. 2V300Ah battery high-temperature float life result
| The battery numbering | ????#1 | ????#2 | ????#3 | ????#4 |
| Float life/unit | ????5 | ????6 | ????9 | ????8 |
Annotate: #1 and #2 are the blank battery of contrast,
#3 and #4 are the battery that has added micro-capsule.
Table 2. 12V10Ah battery cycle life result
| The battery numbering | ????#5 | ????#6 | ????#7 | ????#8 |
| Cycle life/time | ????402 | ????385 | ????726 | ????768 |
Annotate: #5 and #6 are the blank battery of contrast,
#7 and #8 are the battery that has added micro-capsule.
Find by dissection above-mentioned 8 dead battery, the problem that electrolyte is dry and the pole plate growth is elongated has obviously taken place in blank #1, #2 and #5, #6 battery, and #3, #4 and #7, the more blank battery of #8 battery have obvious improvement, so float life and cycle life have obtained significant raising.
Claims (7)
1, a kind of micro capsule for valve controlled sealed lead-acid accumulator is characterized in that cyst wall is the porous solid phase housing that macromolecular material constitutes, and is surrounded by sustained release liquid in the capsule.
2, by the described micro-capsule of claim 1, it is characterized in that micro-capsule forms almost spherical outward, diameter is 10～1000um.
3,, it is characterized in that described macromolecular material is any in the poly-carbon ester of stable existence in strong acid media, polymethyl methacrylate, polyacrylic resin, poly hydroxy ethyl acrylate, the paracyanogen base alkyl acrylate by the described micro-capsule of claim 1.
4, by the described micro-capsule of claim 1, it is characterized in that described sustained release liquid is the deionized water of resistivity greater than 5M Ω cm.
5, by the described micro-capsule of claim 1, it is characterized in that described sustained release liquid is that density is less than or equal to 1.3g/cm
3The analytical pure sulfuric acid aqueous solution.
6, a kind of preparation method by the described micro-capsule of claim 1 is characterized in that comprising in spray drying process, emulsion phase separation method, condensed phase partition method, the water encystation method in the dispersion and water.
7, press the preparation method of the described micro-capsule of claim 6, it is characterized in that described spray drying process is that described macromolecular material is dissolved in the dichloroethanes solvent, solution concentration is 4～6%, then sulfuric acid is added under stirring state, form emulsion, again this emulsion is sprayed in the spray drying tower of 30～40 ℃ of thermal currents, and then make micro-capsule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021128960A CN1177379C (en) | 2002-04-18 | 2002-04-18 | Microcapsule for valve-controlled sealed lead-acid storage battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021128960A CN1177379C (en) | 2002-04-18 | 2002-04-18 | Microcapsule for valve-controlled sealed lead-acid storage battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1404165A true CN1404165A (en) | 2003-03-19 |
| CN1177379C CN1177379C (en) | 2004-11-24 |
Family
ID=4742330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021128960A Expired - Fee Related CN1177379C (en) | 2002-04-18 | 2002-04-18 | Microcapsule for valve-controlled sealed lead-acid storage battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1177379C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110265621A (en) * | 2019-07-22 | 2019-09-20 | 荷贝克电源系统（武汉）有限公司 | Battery |
-
2002
- 2002-04-18 CN CNB021128960A patent/CN1177379C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110265621A (en) * | 2019-07-22 | 2019-09-20 | 荷贝克电源系统（武汉）有限公司 | Battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1177379C (en) | 2004-11-24 |
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| C14 | Grant of patent or utility model | ||
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