CN1286197C - Positive and negative active material for valve-controlled sealed lead-acid battery - Google Patents
Positive and negative active material for valve-controlled sealed lead-acid battery Download PDFInfo
- Publication number
- CN1286197C CN1286197C CNB021382506A CN02138250A CN1286197C CN 1286197 C CN1286197 C CN 1286197C CN B021382506 A CNB021382506 A CN B021382506A CN 02138250 A CN02138250 A CN 02138250A CN 1286197 C CN1286197 C CN 1286197C
- Authority
- CN
- China
- Prior art keywords
- active material
- lead
- positive
- negative electrode
- sealed lead
- 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
- 239000002253 acid Substances 0.000 title claims abstract description 19
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 11
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims abstract description 8
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 19
- 239000011149 active material Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000008961 swelling Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004021 humic acid Substances 0.000 claims description 2
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 238000007711 solidification Methods 0.000 abstract description 6
- 230000008023 solidification Effects 0.000 abstract description 6
- 230000005484 gravity Effects 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000007667 floating Methods 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 230000000007 visual effect Effects 0.000 abstract 1
- 239000011505 plaster Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000006071 cream Substances 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 4
- -1 sodium peroxides Chemical class 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007780 powder milling Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000010998 test method 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
- Battery Electrode And Active Subsutance (AREA)
Abstract
The positive and negative electrode active material for valve controlled sealed lead-acid accumulator features that sodium peroxide is used to replace sulfuric acid in positive and negative electrode lead pastes, proper amount of PTFE is added to positive electrode lead paste, and expanding agent is added to negative electrode lead paste. Because sulfuric acid is not added during paste mixing, the visual specific gravity of the lead paste is lower, the lead paste can be heated and pasted, the porosity of the polar plate is higher, and solidification is not needed, so that the production cost is low, the production efficiency is high, the utilization rate of active substances is improved, and meanwhile, the corrosion of equipment and the environmental pollution are reduced. The prepared battery can be applied to the fields of floating charge use, recycling use and the like.
Description
Technical field
The present invention relates to a kind of lead plaster, belong to the sealed lead acid storage battery technical field as sealed lead acid storage battery positive pole and negative electrode active material.
Background technology
In traditional lead-acid battery production process, used lead powder is crust powder or ball milling powder, lead powder is not pulverous pure plumbous particle, but surface coverage the two-phase body particulate powder thing of the metallic lead of one deck lead oxide, oxidizability is generally between 70～85%, remaining about 15～30% free lead will drop to below 5% until free lead content in further oxidation in follow-up and cream and the solidification process in the lead powder, preferably is no more than 1%.If the free lead content after solidifying in the pole plate will cause to change into difficulty greater than 5%, influence the capacity of pole plate.Solidification process generally needs about 48～72 hours time, and need carry out under the temperature and humidity condition of strictness control.Traditional lead plaster is the mixture of lead powder, sulfuric acid, deionized water and additive, want strict control temperature (can not be higher than 70 ℃) with the cream process, higher with the sulfuric acid density that cream is used, quickened the corrosion to pasting equipment, acid mist has caused the pollution of environment and the harm of operator's physical condition.
Summary of the invention
The purpose of this invention is to provide a kind of shortening production cycle, reduce production costs, reduce environmental pollution, improve the valve controlled sealed lead-acid accumulator positive and negative electrode active material of battery initial capacity and cycle life.
Technical scheme of the present invention is: positive active material is (percentage by weight):
Lead powder 70～80% sodium peroxides 5～10%
Ptfe emulsion 5～8% deionized waters 8～12%
Wherein the concentration of ptfe emulsion is 6%, its role is to increase the adhesion between the active material particle.
Negative electrode active material is (percentage by weight):
Lead powder 70～80% sodium peroxides 5～12%
Swelling agent 3～8% deionized waters 8～10%
Wherein swelling agent is the mixture of barium sulfate, sodium lignosulfonate, humic acid and carbon black, and purpose is to prevent the contraction of negative electrode active material in charge and discharge process.
Sodium peroxide powder plays crucial effects in the above-mentioned both positive and negative polarity active material, and its effect mainly comprises:
1, with the cream process in the free lead in the lead powder is completely oxidized to lead oxide.The chemical reaction that takes place during with cream:
2, the NaOH in the following formula generates sodium sulphate with sulfuric acid reaction in subsequently filling acid and formation process, and the existence of sodium sulphate can refinement be irritated the 4PbOPbSO that forms in the sour process
4Crystal grain, help changing into the carrying out of reaction, thereby both improved the initial capacity (change into then discharge promptly greater than hundred-percent rated capacity for the first time) of battery, guaranteed again than the cycle life of growing.
3, the sodium sulphate that generates in the reaction has increased the activity of ion, has reduced the resistance of charging.
The lead sulfate that forms when 4, the sodium sulphate that generates in the reaction can stop discharge is deposited in the dividing plate, thereby has avoided the generation of lead dendritic crystal short circuit.
Adopt novel lead plaster of the present invention to have following characteristics and advantage as the both positive and negative polarity active material:
(1) can obtain than the lead plaster that hangs down apparent gravity, the apparent gravity of common lead plaster is generally at 3.8g/cm
3～4.2g/cm
3, and the apparent gravity of novel lead plaster can be low to moderate 3.0g/cm
3～3.2g/cm
3, lower lead plaster apparent gravity can improve the porosity of pole plate, therefore can have more sulfuric acid to be diffused into the depths of pole plate, and this has improved the degree of depth of reaction and the utilance of active material greatly.
(2) in traditional lead-acid battery production process,, thereby influence the consistency of cell voltage in groups because the difference of degree of oxidation of lead powder can cause the inhomogeneous of pole plate quality; And do not have free lead basically when adopting novel lead plaster to do electrode active material, thereby guaranteed the homogeneity of pole plate.
(3) can simplify production process, the reduction production time.Solidifying in traditional lead-acid battery production process is one extremely important and essential step, make electrode active material if adopt novel lead plaster, then can omit in the solidification process steps such as crystallization again of the oxidation of free lead and basic lead sulphate in the lead plaster, shortened the time of solidification process greatly, the cycle of producing battery is shortened, thereby saved electric energy, manpower and equipment depreciation etc. that traditional very long solidification process consumes, reduced production cost.
Can be when (4) adopting novel lead plaster to be coated with cream without sulfuric acid as active material, thus avoid producing a large amount of heats, alleviated the corrosion of sulfuric acid to equipment, saved and the cream time.
Embodiment
Embodiment 1: press following composition (percentage by weight, down together): lead powder 80%, Na
2O
25%, polytetrafluoroethylene 5%, deionized water 10% carry out positive pole and cream, earlier lead powder and sodium peroxide powder are mixed stirring 3 minutes, then adding ptfe emulsion stirred 5 minutes, add deionized water then, fully stirred 30 minutes, can coat positive plate; Press following composition: lead powder 77%, Na
2O
28%, swelling agent 5%, deionized water 10% carry out negative pole and cream, earlier lead powder and sodium peroxide powder are mixed stirring 3 minutes, then add swelling agent and stir 5 minutes, add deionized water then, fully stir 30 minutes, can coat negative plate.The pole plate that coats can be without curing, at room temperature dry 10～12h or in 60 ℃ drying room dry 4～6h can enter assembling and be internalized into operation, remaining technology can adopt the production technology of present valve controlled sealed lead-acid accumulator fully.The valve controlled sealed lead-acid accumulator that is assembled into 2V200Ah carries out performance test, 10h leads gravimetric specific energy and has reached 33.9Wh/kg, 1h leads gravimetric specific energy and has reached 24.5Wh/kg, 100%DOD cycle life has reached 300 times, and all the other every performance index all satisfy the regulation among the YD/T799-1996 " communication valve-control sealed lead acid battery specification requirement and test method ".The result proves, adopt the valve controlled sealed lead-acid accumulator of both positive and negative polarity active material of the present invention preparation can be applied in floating charge fully and the field such as use and recycle, reduced production cost simultaneously, shortened the production time, compare with adopting common active material, can save the time of 40h～50h.
Embodiment 2,3 only changes the positive and negative electrode active material, as following table:
| Embodiment | Positive active material % | Negative electrode active material % | ||||||
| Lead powder | Na 2O 2 | Polytetrafluoroethylene | Deionized water | Lead powder | Na 2O 2 | Swelling agent | Deionized water | |
| 2 | 76 | 7 | 6 | 11 | 74 | 12 | 6 | 8 |
| 3 | 72 | 10 | 8 | 10 | 75 | 11 | 5 | 9 |
Claims (4)
1, a kind of valve controlled sealed lead-acid accumulator positive active material, comprise lead powder, deionized water, it is characterized in that containing in the active material sodium peroxide, ptfe emulsion, the percentage by weight of each composition in the active material total amount is: lead powder 70～80%, sodium peroxide 5～10%, ptfe emulsion 5～8%, deionized water 8～12%.
2, by the described valve controlled sealed lead-acid accumulator positive active material of claim 1, the concentration that it is characterized in that ptfe emulsion is 6%.
3, a kind of valve-control sealed lead acid battery negative electrode active material, comprise lead powder, deionized water, it is characterized in that containing in the active material sodium peroxide, swelling agent, the percentage by weight of each composition in the active material total amount is: lead powder 70～80%, sodium peroxide 5～12%, swelling agent 3～8%, deionized water 8～10%.
4, by the described valve controlled sealed lead-acid accumulator negative electrode active material of claim 3, it is characterized in that described swelling agent is the mixture of barium sulfate, sodium lignosulfonate, humic acid and carbon black.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021382506A CN1286197C (en) | 2002-09-11 | 2002-09-11 | Positive and negative active material for valve-controlled sealed lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021382506A CN1286197C (en) | 2002-09-11 | 2002-09-11 | Positive and negative active material for valve-controlled sealed lead-acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1482695A CN1482695A (en) | 2004-03-17 |
| CN1286197C true CN1286197C (en) | 2006-11-22 |
Family
ID=34147187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021382506A Expired - Fee Related CN1286197C (en) | 2002-09-11 | 2002-09-11 | Positive and negative active material for valve-controlled sealed lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1286197C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101882681A (en) * | 2010-06-21 | 2010-11-10 | 冯家齐 | Positive and negative plate additive of lead-acid accumulator and preparation method thereof |
| CN103000883A (en) * | 2012-12-26 | 2013-03-27 | 江苏苏中电池科技发展有限公司 | Formula of positive active material for lead-acid power battery and preparation method of positive active material |
| CN103633331A (en) * | 2013-11-28 | 2014-03-12 | 江苏科能电源有限公司 | Positive active material for lead-acid power battery and preparation method of positive active material |
| CN103779557B (en) * | 2014-01-03 | 2016-01-27 | 河北超威电源有限公司 | A kind of electric boosted automobile-used low temperature resistant lead accumulator lead plaster and preparation method thereof |
| 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 |
| CN112002876B (en) * | 2020-07-23 | 2022-03-01 | 天能电池集团股份有限公司 | Quick manufacturing process for lead storage battery pole plate |
-
2002
- 2002-09-11 CN CNB021382506A patent/CN1286197C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1482695A (en) | 2004-03-17 |
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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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061122 Termination date: 20110911 |