CN1177379C - Micro capsule for valve controlled sealed lead-acid accumulator and its prepn - Google Patents
Micro capsule for valve controlled sealed lead-acid accumulator and its prepn Download PDFInfo
- Publication number
- CN1177379C CN1177379C CNB021128960A CN02112896A CN1177379C CN 1177379 C CN1177379 C CN 1177379C CN B021128960 A CNB021128960 A CN B021128960A CN 02112896 A CN02112896 A CN 02112896A CN 1177379 C CN1177379 C CN 1177379C
- Authority
- CN
- China
- Prior art keywords
- capsule
- micro
- battery
- acid
- 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.)
- Expired - Fee Related
Links
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
The present invention relates to a micro capsule for a valve controlled sealed lead-acid accumulator and a preparation method thereof, which is characterized in that a capsule wall is a solid phase porose shell body formed by macromolecular materials, and deionized water or sulphuric acid electrolyte is filled in an inner pack of the capsule; the preparation method generally uses a spray drying method. The micro capsule made by the present invention is filled in a part of or all gaps in an accumulator. On one hand, the deformation expansion of a pole plate can be prevented, and on the other hand, the dehydration of the accumulator in use can be replenished. Thus, the service life of the lead-acid accumulator is greatly prolonged, wherein floating charge service is prolonged by 60 %, and cyclic life is prolonged by 80 %.
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: the cyst wall of micro capsule for valve controlled sealed lead-acid accumulator is the porous solid phase housing that macromolecular material constitutes, and is surrounded by resistivity in the capsule and is less than or equal to 1.3g/cm greater than deionized water or the density of 5M Ω cm
3The analytical pure sulfuric acid aqueous solution.
Above-mentioned micro-capsule forms almost spherical outward, and diameter is 10～1000 μ m.Macromolecular material is any in the Merlon of stable existence in strong acid media, polymethyl methacrylate, polyacrylic acid resin, poly hydroxy ethyl acrylate, the paracyanogen base alkyl acrylate.
Technical scheme of the present invention also comprises the preparation method of described micro-capsule, and this method is to adopt in spray drying process, emulsion phase separation method, condensed phase partition method, the water one of method in the 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%, and this has strengthened the market competitiveness of valve controlled sealed lead-acid accumulator greatly.
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 (5)
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 resistivity in the capsule and is less than or equal to 1.3g/cm greater than deionized water or the density of 5M Ω cm
3The analytical pure sulfuric acid aqueous solution.
2, by the described micro-capsule of claim 1, it is characterized in that micro-capsule forms almost spherical outward, diameter is 10～1000 μ m.
3,, it is characterized in that described macromolecular material is any in the Merlon of stable existence in strong acid media, polymethyl methacrylate, polyacrylic acid resin, poly hydroxy ethyl acrylate, the paracyanogen base alkyl acrylate by the described micro-capsule of claim 1.
4, a kind of preparation method by the described micro-capsule of claim 1 is characterized in that adopting in spray drying process, emulsion phase separation method, condensed phase partition method, the water one of method in the encystation method in the dispersion and water.
5, press the preparation method of the described micro-capsule of claim 4, 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 | Micro capsule for valve controlled sealed lead-acid accumulator and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021128960A CN1177379C (en) | 2002-04-18 | 2002-04-18 | Micro capsule for valve controlled sealed lead-acid accumulator and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1404165A CN1404165A (en) | 2003-03-19 |
| CN1177379C true 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 | Micro capsule for valve controlled sealed lead-acid accumulator and its prepn |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1177379C (en) |
Families Citing this family (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
Also Published As
| Publication number | Publication date |
|---|---|
| CN1404165A (en) | 2003-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110010863A (en) | A kind of method of lithium ion battery negative material prelithiation | |
| CN107221716A (en) | A kind of chargeable water system Zinc ion battery | |
| CN103181003B (en) | Electrode slice and preparation method thereof and ultracapacitor and lithium ion battery | |
| CN113270577B (en) | Aqueous zinc ion battery and positive electrode material | |
| CN110148735A (en) | A kind of preparation method of self-supporting graphite phase carbon nitride/conducting polymer composite sulfur positive electrode | |
| CN106384674A (en) | Aqueous rechargeable sodium-ion capacitor battery based on titanium phosphorus oxide cathode material | |
| CN110010373A (en) | A kind of embedding zinc processing method of electrode and its application in the preparation of cell type supercapacitor | |
| CN108899528A (en) | A kind of lithium ion battery negative material P+TiO2The preparation method of+CNT | |
| CN114551869B (en) | Lithium phosphomolybdate nanorod lithium battery positive electrode material, and preparation method and application thereof | |
| CN111646510A (en) | High-rate titanium niobium oxide microsphere and preparation method and application thereof | |
| CN105845991A (en) | Spirally wound lead-carbon storage battery for starting and stopping of automobile | |
| CN101521284A (en) | Lithium-iron disulfide disposable column type battery and preparation process thereof | |
| CN109167104A (en) | A kind of room temperature sodium-sulphur battery and preparation method thereof | |
| CN1177379C (en) | Micro capsule for valve controlled sealed lead-acid accumulator and its prepn | |
| US5378550A (en) | Electrolytes for power sources | |
| CN201072785Y (en) | High power alkaline zinc-manganese battery | |
| CN115763789A (en) | Flexible water-based zinc ion battery, positive electrode material and preparation method thereof | |
| CN111816853B (en) | CuS-Cu7.2S4Nanocomposite, lithium battery and preparation method | |
| CN111403721B (en) | Preparation method of lithium titanate negative electrode material of lithium ion battery | |
| CN113140721A (en) | Self-supporting aluminum ion battery positive electrode material, preparation method thereof and aluminum-air battery | |
| CN111554916A (en) | Quasi-solid state flexible Na-O2Room temperature secondary battery and preparation method thereof | |
| CN105529455B (en) | A kind of spherical SnO of prism assembling2Anode material of lithium-ion battery and preparation method thereof | |
| CN1870344A (en) | Battery chemical component negative pressure processing method of glass fibre adsorption valve control battery | |
| CN105140574B (en) | A kind of Ni-MH power cell and preparation method thereof | |
| CN205595382U (en) | A lithium cell group for wireless hand vacuum cleaner |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |