CN101388469B - Valve controlled type lead acid battery without maintenance - Google Patents
Valve controlled type lead acid battery without maintenance Download PDFInfo
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- CN101388469B CN101388469B CN2007100128359A CN200710012835A CN101388469B CN 101388469 B CN101388469 B CN 101388469B CN 2007100128359 A CN2007100128359 A CN 2007100128359A CN 200710012835 A CN200710012835 A CN 200710012835A CN 101388469 B CN101388469 B CN 101388469B
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- battery
- valve
- acid battery
- maintenance
- lead
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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
Abstract
The invention relates to a valve-regulated maintenance-free lead-acid battery, which comprises positive and negative plates, an active matter and electrolyte. The invention is characterized in that the valve-regulated maintenance-free lead-acid battery chooses a metal-catalyzed membrane to be the anode and the cathode of a battery, utilizes the weight of the active matters as cardinal number, adds 0.5%-15% copper base soil chromium nitride or nickel base rare earth titanium nitride catalytic membrane particles, and chooses polyolefin base materials to be made into a separation membrane which is fixed on a valve control portion to form a separation membrane control valve, and the bore diameter of the separation membrane is 50-400 nanometer, and the factor of porosity is 30-60%. The valve-regulated maintenance-free lead-acid battery improves the electrical conductivity of electrode reaction products of lead compounds and PbSO and the like in lead paste, increases the surface areas of active matters, improves the operating factor of active matters, and has better mechanical, electrical continuity and acid collecting functions. The valve-regulated maintenance-free lead-acid battery utilizes the separation membrane which has the advantages of high temperature resistance, chemical resistance, high mechanical strength, big infiltration capacity, excellent separating property, long service span and the like to be a battery control valve, which guarantees the accuracy of gas-liquid separation, and plays the catalytic function to oxy-hydrogen combination of electrochemical reaction of batteries. A catalyst membrane is used in the polar plate of a battery, which improves the operating factor of lead, and reduces the number of slab lattices.
Description
Technical field:
Present technique relates to positive and negative pole plate preparation technology, the manufacturing process of film lead acid accumulator, particularly valve-regulated lead-acid battery technology of making valve-controlled lead-acid accumulator plate.
Background technology:
Lead-acid battery has a wide range of applications in each field of industrial or agricultural, yet it is lower that lead acid accumulator also exists specific energy at present, the shortcoming that cycle life is short, lead, acid pollution in the production application have simultaneously not only destroyed environment, and have had a strong impact on health condition of people.
Valve controlling sealed lead accumulator has obtained using widely with its excellent properties such as pollution-free, long service life, easy maintenance, yet the off-capacity that valve controlled sealed lead-acid accumulator is come out in actual use, specific energy is low, the premature capacity loss phenomenon is obvious, the life-span is short etc., and problems also should in time solve.
Improve the lead acid accumulator performance, work is omnibearing, from grid make, active matter is produced, electrolyte is constituted to battery structure etc., and everyway is constantly dissolving in new technology, new material.Positive active material as the lead acid accumulator heart is studied at most by numerous experts and scholars.Be performance that improves lead acid battery positive electrode and the useful life that prolongs battery, for a long time, people extremely pay attention to studying the influence of anode additive to positive electrode active material utilization.For example, add conductive carbon cellulosic material such as carbon fiber, anisotropy graphite and acetylene carbon black for improving cathode performance, interpolation rare-earth metal material etc. has all been obtained patent.But these technique effects are not very remarkable, and it is also few that present suitability for industrialized production is used.Main cause is that lead acid battery positive electrode has a large amount of Pb02 and PbS04, and Pb02 has very strong oxidizability and high anode current potential characteristics, the oxidized gradually inefficacy of these technical measures; PbS04 is insulator or semiconductor, electrochemical reaction when taking place in lead acid accumulator, the PbS04 crystal is constantly grown up, and makes that the electrode duct is blocked, active material softens too early, comes off or battery failure, thereby to the discharge performance of lead-acid battery with cause bigger influence useful life.Battery structure research also is a large amount of, particularly valve control battery from the valve body structure to oxygen, that hydrogenation such as closes at research is more.The valve control battery control valve is the valve control battery vitals, and its performance quality, reliable operation degree and battery life etc. have bigger relation.Present battery control valve is divided into mechanical type and rubber type two big classes substantially, and operation principle is identical, is gas concentrations such as the oxygen that produces when carrying out electrochemical reaction of battery, hydrogen, carbon dioxide substantially to a certain degree the time, and valve is opened automatically and emitted gas.The problem that this this control valve exists is that when gas was discharged, steam, acid solution also had certain discharge, made battery become dry to dry up and scrapped.
Summary of the invention:
The present invention is directed to the problem that valve-regulated lead-acid battery exists at present, overflow, set up aspect such as gas passage and take technical measures from improving pole board oxidation, prevent that the electrode duct from blocking and suppressing steam, acid solution, a kind of high specific energy, high power, long-life, anti-overdischarge and valve controlled type lead acid battery without maintenance that can quick charge are provided.
Technical conceive of the present invention be with the metal-based catalyzed application of membrane in anode, by the effect of catalytic membrane, improve the pole board oxidation degree, promote electrochemical reaction rates, extending battery life; Also organic ultrafiltration membrane technique is applied to the battery positive and negative electrode, prevents that by the milipore filter effect electrode duct from blocking, active material softens too early, comes off, and prevents battery failure, improve battery performance.The present invention also is applied to the micropore technology make the present invention become real lead acid battery without maintenance in the both positive and negative polarity, control valve of valve-regulated lead-acid battery.Storage battery of the present invention comprises positive/negative plate, active material and electrolyte, it is characterized in that choosing adds the metal catalytic film and makes battery plus-negative plate, with active material weight is that radix adds 0.5～15% copper base soil chromium nitride catalytic membrane particle, select for use polyolefin-based materials to make diffusion barrier and be fixed in valve controlled position formation diffusion barrier control valve, this diffusion barrier aperture is 50～400 nanometers, porosity 30～60%.The present invention's choosing adds the metal catalytic film and makes battery plus-negative plate, can also active matter weight be that radix adds 0.5～15% Ni-based rare earth titanium nitride catalytic membrane particle, select for use polyolefin-based materials to make diffusion barrier and be fixed in valve controlled position formation diffusion barrier control valve, this diffusion barrier aperture is 50～400 nanometers, porosity 30～60%.
Cell manufacturing method of the present invention is as follows:
One, catalytic membrane manufacturing
With the macromolecule foam is that carrier passes through vacuum ionic electroplating method making copper base rare earth chromium nitride or Ni-based rare earth titanium nitride catalytic membrane.Concrete grammar is:
(1), particulate is inlayed.Add the method for filling by machinery the copper of several microns to tens microns of diameters or nickel particle and rare earth particulate (are the lanthanide rare metal oxide, 0.5～3%) be mounted in the macromolecule foam carrier mesh, reach the uniformity that film thickness is inlayed firmly and guaranteed to prepare subsequently to particulate again through drum extrusion;
(2), particulate combination.Get 3～5 microns chromium film or titanium film inlaying on the matrix of particulate plating, make and inlay particulate and the net matrix bond is an one;
(3), catalytic membrane is set up.On micropore metal net matrix, deposit the copper base rare-earth nano-crystal chromium nitride film or the Ni-based rare earth sodium rice crystalline titanium nitride film of 3-5 micron thickness by physical vapor deposition;
(4), catalytic membrane is made particulate material by mechanical means and mix in the battery positive and negative electrode active matter of the cream of becoming reconciled admixture ratio 0.5-15% (weight ratio).
This film can significantly improve the electricity of electrode reaction such as lead compound and PbS0 in the lead plaster and lead, has mechanical continuity and electric continuity in active matter, effectively avoid battery failure, has improved the dark circulation ability and the useful life that has prolonged battery of battery.Make battery pole plates with this.
Two, diffusion barrier manufacturing
Diffusion barrier adopts plate armature, and thickness is appropriateness evenly, is raw material with high molecular polymer such as polyethylene, 150～400 molecular weight polyethylenes, polytetrafluoroethylene, high density polyethylene, adds expanding agent, forming agent etc..With the moulding of pressure sintering method.Require the filter opening normal distribution, perforate is even, and filter opening is the honeycomb mesh, good mechanical performance.Have the toughness and the elasticity of higher intensity and rigidity, appropriateness, impact resistance is good.This film is a ultrafiltration character, and the aperture is in the 50-400 nanometer, between the porosity 30-60%.Change with battery sizes, air displacement.This diffusion barrier is rational in infrastructure, the aperture even, can effectively tackle the sulfuric acid that other means are difficult to reclaim in the electrolyte, but can remove gases such as unnecessary hydrogen, oxygen, carbon dioxide.
Three, battery manufacturing.
Make storage battery and diffusion barrier is fixed in the exhaust valve positions of battery by traditional approach.This valve has gas, liquid centrifugation, under certain pressure, can discharge gas and liquid can not be discharged.
Use catalytic membrane to constitute of the present invention one big characteristics in the battery active matter, the character of catalytic membrane is plyability, but it must collect following effects one or more.The one, improved the conductivity of electrode reaction such as lead compound and PbS0 product in the lead plaster, the 2nd, increase the active matter surface area, improve the active matter utilance, the 3rd, mechanical preferably continuity and electric continuity, the 4th are arranged, have collection acid effect.It is another feature of the present invention that the diffusion barrier technology is applied to battery.Characteristics such as membrane separation technique is efficient with it, energy-saving and environmental protection and molecular level filtration, fields such as water treatment, chemical industry, electronics, medicine, food processing have been widely used in, but it is that use at battery industry and few, that this diffusion barrier has is high temperature resistant, resistance to chemical attack, mechanical strength height, anti-microbe ability is strong, infiltration capacity is big, clanability is strong, pore-size distribution is narrow, separating property is good and characteristics such as long service life, as battery control valve, can guarantee the accuracy that gas, liquid separate, can close catalytic action to the oxygen hydrogenation of cell electrochemical reaction again.
Catalytic membrane is applied in the battery pole plates, has improved plumbous utilance, thereby reduced grid quantity.The battery of the embodiment of the invention one has used 4 formal negative plates, and control cell 7 positive 8 negative plates.The comprehensive technical indexes of film battery but is higher than control cell.
Embodiment
Following specific embodiment.
Embodiment 1
With the macromolecule foam is that carrier passes through vacuum ionic electroplating method making copper base rare earth chromium nitride battery catalytic membrane.Concrete grammar is: (1), add the method for filling by machinery the copper particulate and the rare earth particulate of several microns to tens microns of diameters is mounted in the macromolecule foam carrier mesh reaches the uniformity that film thickness is inlayed firmly and guaranteed to prepare subsequently to particulate again through drum extrusion.(2) by galvanoplastic, get several microns plumbous film inlaying on the matrix of particulate plating, make and inlay particulate and the net matrix bond is an one.(3) on the basis of the above, on micropore metal net matrix, deposit the nano-crystal chromium nitride film of 3-5 micron thickness by physical vapor deposition.Catalytic membrane is made particulate material by mechanical means mix in the battery positive and negative electrode active matter of the cream of becoming reconciled, admixture ratio 0.6% (weight ratio) is made pole plate and is carried out the battery assembling with traditional handicraft.At battery valve controlled position hot pressing control valve, make the 12V10Ah battery during assembling.
Embodiment 2
With the macromolecule foam is that carrier passes through the vacuum ionic electroplating method and makes Ni-based rare earth titanium nitride battery catalytic membrane, catalytic membrane is made particulate material by mechanical means mixes in the battery positive and negative electrode active matter of the cream of becoming reconciled, admixture ratio 5% (weight ratio) is made pole plate and is carried out the battery assembling with traditional handicraft.At battery valve controlled position hot pressing control valve, make the 12V10Ah battery during assembling.
Embodiment 3
With the macromolecule foam is that carrier passes through vacuum ionic electroplating method making copper base rare earth chromium nitride battery catalytic membrane, catalytic membrane is made particulate material by mechanical means mixes in the battery positive and negative electrode active matter of the cream of becoming reconciled, admixture ratio 15% (weight ratio) is made pole plate and is carried out the battery assembling with traditional handicraft.At battery valve controlled position hot pressing control valve, make the 12V10Ah battery during assembling.
Through actual measurement, it is 16.26Ah that the storage battery of numbering 1 is surveyed 5 hour rate capacity, active material utilization 41%, and gravimetric specific energy 48.6Wh/Kg, 3.7 kilograms of total cell weight, the 55%DOD circulation has reached 499 times.
It is 17.94Ah that the storage battery of numbering 2 is surveyed 5 hour rate capacity, active material utilization 43.2%, and gravimetric specific energy 48.6Wh/Kg,, 3.7 kilograms of total cell weight, the 55%DOD circulation has reached 518 times.
It is 19.52Ah that the storage battery of numbering 3 is surveyed 5 hour rate capacity, active material utilization 48.52%, and gravimetric specific energy 48.6Wh/Kg,, 3.7 kilograms of total cell weight, the 55%DOD circulation has reached 580 times.
Claims (4)
1. valve controlled type lead acid battery without maintenance, comprise positive/negative plate, active material and electrolyte, it is characterized in that choosing adds the metal catalytic film and makes battery plus-negative plate, with active material weight is that radix adds 0.5～15% copper base rare earth chromium nitride catalytic membrane particle, select for use polyolefin-based materials to make diffusion barrier and be fixed in valve controlled position formation diffusion barrier control valve, this diffusion barrier aperture is 50～400 nanometers, porosity 30～60%.
2. valve controlled type lead acid battery without maintenance, comprise positive/negative plate, active material and electrolyte, it is characterized in that choosing adds the metal catalytic film and makes battery plus-negative plate, with active material weight is that radix adds 0.5～15% Ni-based rare earth titanium nitride catalytic membrane particle, select for use polyolefin-based materials to make diffusion barrier and be fixed in valve controlled position formation diffusion barrier control valve, this diffusion barrier aperture is 50～400 nanometers, porosity 30～60%.
3. according to claim 1 or 2 described valve controlled type lead acid battery without maintenance, it is characterized in that the polyolefin-based materials of selecting for use is polyethylene or polytetrafluoroethylene.
4. according to the described valve controlled type lead acid battery without maintenance of claim 3, it is characterized in that described polyethylene is selected from 150～400 molecular weight polyethylenes or high density polyethylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100128359A CN101388469B (en) | 2007-09-11 | 2007-09-11 | Valve controlled type lead acid battery without maintenance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100128359A CN101388469B (en) | 2007-09-11 | 2007-09-11 | Valve controlled type lead acid battery without maintenance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101388469A CN101388469A (en) | 2009-03-18 |
| CN101388469B true CN101388469B (en) | 2010-04-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2007100128359A Expired - Fee Related CN101388469B (en) | 2007-09-11 | 2007-09-11 | Valve controlled type lead acid battery without maintenance |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114094203A (en) * | 2021-10-29 | 2022-02-25 | 河南润祥能源科技有限公司 | Olefin double-carbon energy storage square cabin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149266A (en) * | 1994-03-30 | 1997-05-07 | 尖端研究组织公司 | Improved energy storage device and methods of manufacture |
| CN1476118A (en) * | 2002-08-13 | 2004-02-18 | 江苏隆源双登电源有限公司 | Deep circulation plato grid alloy formulation for lead acid battery positive electrode |
-
2007
- 2007-09-11 CN CN2007100128359A patent/CN101388469B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149266A (en) * | 1994-03-30 | 1997-05-07 | 尖端研究组织公司 | Improved energy storage device and methods of manufacture |
| CN1476118A (en) * | 2002-08-13 | 2004-02-18 | 江苏隆源双登电源有限公司 | Deep circulation plato grid alloy formulation for lead acid battery positive electrode |
Non-Patent Citations (2)
| Title |
|---|
| 朱松然等.一种抑制正极活性物质软化的稀土化合物.电池工业6 4.2001,6(4),全文. |
| 朱松然等.一种抑制正极活性物质软化的稀土化合物.电池工业6 4.2001,6(4),全文. * |
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| CN101388469A (en) | 2009-03-18 |
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Granted publication date: 20100414 Termination date: 20170911 |