CN100557863C - Lead-acid storage battery and paste mixing process for electric moped - Google Patents
Lead-acid storage battery and paste mixing process for electric moped Download PDFInfo
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- CN100557863C CN100557863C CNB2005100956730A CN200510095673A CN100557863C CN 100557863 C CN100557863 C CN 100557863C CN B2005100956730 A CNB2005100956730 A CN B2005100956730A CN 200510095673 A CN200510095673 A CN 200510095673A CN 100557863 C CN100557863 C CN 100557863C
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- battery
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- storage battery
- acid storage
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- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000002253 acid Substances 0.000 title claims abstract description 14
- 230000008569 process Effects 0.000 title claims abstract description 11
- 238000003860 storage Methods 0.000 title claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000725 suspension Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000006230 acetylene black Substances 0.000 claims abstract description 8
- 239000011505 plaster Substances 0.000 claims description 13
- 239000006071 cream Substances 0.000 claims description 11
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000005543 nano-size silicon particle Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229920005610 lignin Polymers 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 abstract 2
- 229910002804 graphite Inorganic materials 0.000 abstract 1
- 239000010439 graphite Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000007774 positive electrode material 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
- 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 description 1
- 206010011906 Death Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002224 dissection Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005303 weighing 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Battery Electrode And Active Subsutance (AREA)
Abstract
A lead-acid storage battery paste mixing process for an electric power-assisted vehicle belongs to a manufacturing method of a lead-acid storage battery. The method is characterized in that special suspension is added during paste mixing: nano-scale silicon dioxide and colloidal graphite are added into the suspension used by the anode; acetylene black was added to the suspension used for the negative electrode. The suspension was added 5 minutes after the addition of pure water and before the addition of sulfuric acid. The battery adopting the paste mixing process has the advantages that on the premise of not changing the structure and the cycle life of the battery, the lead dioxide content of the formed positive electrode plate is more than 85 percent, under the environment of 25 ℃, the rated discharge time of a 36v10Ah battery pack from 5A to 31.5v is more than 150 minutes, the weight ratio energy reaches more than 36.40wh/Kg, and the battery is obviously improved compared with the existing lead-acid storage battery of the same type.
Description
Technical field
The present invention relates to a kind of electric boosted automobile-used lead acid accumulator and cream technique, belong to the lead acid accumulator manufacture method.
Background technology
Along with the continuous expansion of Moped Scooter volume of production and marketing, the demand of electric boosted automobile-used lead acid accumulator increases day by day.People wait in expectation as the battery of power resources, and weight is light more good more and capacity is the bigger the better, and the gravimetric specific energy of electric boosted Vehicular battery has been proposed more and more higher requirement.With the 12v10Ah battery is example, the electric boosted automobile-used lead acid accumulator product of this model in current market, and general weight is (4.2～4.3) Kg/, gravimetric specific energy is confined to (27.84～28.56) Wh/Kg.
Thereby the active material utilization of battery improves in many enterprises by the pole plate assembling slice number in the attenuate battery grid increase cell negative terminal.But increase in single lattice behind the pole plate assembling slice number, because the corresponding increase of weight ratio that in battery, occupies as the grid of conducting matrix grain, the gravimetric specific energy of battery has been difficult to raising, and the electric vehicle battery design is gone up this as thin pole plate assembling, be subjected to the restriction of mechanical strength deficiency behind the grid attenuate, further the possibility of attenuate grid is very limited.Behind the attenuate grid, the processing effect of same battery is lowered, because the grid intensity decreases, the scrappage of pole plate is also very high in the manufacture process.Other enterprises by with the cream process in, the content that increases sulfuric acid in the lead plaster improves the initial capacity of battery, to reach higher gravimetric specific energy, but because too high acid content in the lead plaster, cause the easier softening and shedding of positive active material, the easier salinization of negative electrode active material loses activity, and the cycle life of battery descends significantly.How under the prerequisite that does not influence other performances, improve the gravimetric specific energy of electric boosted Vehicular battery, drop into, reduce environmental pollution saving national resources input and consumer individual, all having realistic meaning, is the problem that each battery manufacturer man very pays close attention to.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of under the prerequisite that does not change battery structure and cycle life, improve electric boosted automobile-used lead acid accumulator gravimetric specific energy and cream technique.
Technical scheme of the present invention is: be primary raw material with the lead powder, successively add additive, pure water, sulfuric acid and make lead plaster, improvements be with the cream process in add suspension and mix, to the raw material of every 100kg lead powder, add 3～4L suspension, the proportioning of described suspension is:
Anodal suspension: deionized water 100kg, nano silicon 9.5～10.5kg, aquadag 5～10kg, ptfe emulsion 9.5～10.5kg of 60%;
Negative pole suspension: deionized water 100kg, acetylene black 4.5～5.5kg, lignin 5～6kg, carbon black 14.5～15.5kg.
In the above-mentioned and cream process adding of suspension after adding pure water and stirring 5 minutes with adding sulfuric acid before.
In the above scheme, the aquadag of adding, nano silicon and acetylene black have high dispersiveness, are convenient to be distributed in the middle of the lead plaster as far as possible uniformly.Aquadag is a resistance to oxidation conductive carbon cellulosic material, improves the electric conductivity of battery positive electrode active material effectively; Nano silicon is converted into silica gel in sulfuric acid solution, play H in the process of battery chemistries reaction
+Complexing-the release action of ion, the part orthosilicic acid of Xing Chenging is dissolved simultaneously enter solution after, the microscopic void that stays in lead plaster has increased the reaction surface of anode.By the even adding of aquadag and nano silicon, improved the chemical property of anode, improved the specific energy of anode.The acetylene black of polymolecularity adds after the negative pole, can play the effect of swelling agent, further improves the true specific area of cathode lead plaster.Because acetylene black is not dissolved substantially, therefore in the course of reaction of battery, can not move the negative interaction that produces other, and acetylene black plays catalytic action to the oxidation of lead, can promote plumbous oxidation in the polar plate solidification process in the negative pole better, improve the active material utilization of negative pole.Be chosen in the adding pure water and drop into both positive and negative polarity suspension after 5 minutes and before adding sulfuric acid, be because on the one hand this moment, lead plaster was moistening fully and mix through pure water, the lead powder part can not take place absorb suspension fully and cause the local problem of assembling of additive; On the other hand, after preventing to add sulfuric acid, will form the crystallization of basic lead sulphate in the lead plaster, the suspension composition of interpolation is difficult to enter crystallization inside.
Embodiment
Be example with the most frequently used 6-DZM-10 battery of Moped Scooter below, concrete introduce improve electric boosted automobile-used lead acid accumulator gravimetric specific energy and cream technique.
At first, supending: remove ionized water 100kg, nano silicon 10kg, aquadag 8kg, 60% ptfe emulsion 10kg, mix to stir and make anodal suspension; Remove ionized water 100kg, acetylene black 5kg, lignin 5.5kg, carbon black 15kg again, mix to stir and make negative pole suspension.Then and the system positive and negative pole lead paste: according to the form below takes by weighing lead powder, pure water, sulfuric acid and associated additives, routinely with cream technique and the system positive and negative pole lead paste:
| Raw material | The anode diachylon proportional quantity | The cathode lead plaster proportional quantity |
| Lead powder | 100Kg | 100Kg |
| Red lead | 12.5Kg | 0 |
| Short fiber | 0.07Kg | 0.07Kg |
| Pure water | 6.5 rise | 6.5 rise |
| Sulfuric acid (1.4g/ml) | 7.2 rise | 7 liters |
| Barium sulfate | 0 | 0.7Kg |
| Lignin | 0 | 0.1Kg |
| Humic acid | 0 | 0.3Kg |
| Carbon black | 0 | 0.3Kg |
| Regulate water | 0～4L | 0～4L |
With the cream process in add pure water and stir 5 minutes after with add sulfuric acid before, respectively positive and negative electrode suspension 3.5L is dropped into and system in the positive and negative electrode lead plaster.The apparent gravity of control anode diachylon is (4.35～4.45) g/ml, and the apparent gravity of control cathode lead plaster is (4.45～4.55) g/ml.
According to cell manufacturing method the lead plaster of making is made pole plate and is assembled into 48 on 6-DZM-10 battery below,, further specify effect of the present invention by detecting contrast.Inject 1.235g/ml in battery, 25 ℃ analytical pure sulfuric acid solution (interior contains sodium sulfate 18g/L), single lattice are annotated the acid amount and are 128ml, change into three stages charging standard then.Changing into used equipment is 450v15A high-frequency high-power power supply.After changing into end, carry out combo according to the final voltage of battery capacity detection and the open circuit voltage of battery.Per 3 batteries are formed the battery pack of one group of 36v series, can join 16 groups.Get wherein 3 batteries dissections, analyze the brown lead oxide content in the anode plate.Actual detected result is: wherein pole plate top content is 88.3%, and the middle part is 87.2%, and the bottom is 86%, and the detection data show that the formation efficiency of battery is higher and formation effect is more even up and down.With the volumetric precipitation method analysis, testing result is 1.352g/ml, 25 ℃ to the sulfuric acid concentration in the glass fibre separator.
Remaining 15 Battery packs are placed in 25 ℃ ± 2 ℃ the environment, till being discharged to whole group termination voltage 31.5v with constant current 5A, the discharge time of battery is all more than 150 minutes, gravimetric specific energy is greater than 36.40Wh/Kg, prolong about 10～12 minutes discharge time than normal battery, and the Capacity Ratio between the battery pack is more approaching.
The particular capacity testing result is as follows:
| Group number | Discharge time (min) | Discharge capacity (Ah) | Battery weight (Kg) | Gravimetric specific energy (Wh/Kg) | Group number | Discharge time (min) | Discharge capacity (Ah) | Battery weight (Kg) | Gravimetric specific energy (Wh/Kg) |
| 1 | 152 | 12.67 | 4.22 | 36.03 | 9 | 156 | 13.00 | 4.24 | 36.79 |
| 2 | 154 | 12.83 | 4.23 | 36.40 | 10 | 155 | 12.92 | 4.22 | 36.74 |
| 3 | 154 | 12.83 | 4.21 | 36.57 | 11 | 153 | 12.75 | 4.20 | 36.43 |
| 4 | 151 | 12.58 | 4.23 | 35.69 | 12 | 152 | 12.67 | 4.20 | 36.20 |
| 5 | 155 | 12.92 | 4.24 | 36.57 | 13 | 157 | 13.08 | 4.23 | 37.11 |
| 6 | 155 | 12.92 | 4.22 | 36.74 | 14 | 151 | 12.58 | 4.21 | 35.86 |
| 7 | 153 | 12.75 | 4.21 | 36.34 | 15 | 154 | 12.83 | 4.22 | 36.48 |
| 8 | 157 | 13.08 | 4.24 | 37.02 |
From above-mentioned battery, get the parallel comparison of 2 Battery packs with normal battery, in 25 ℃ ± 2 ℃ environment,,, constitute Rapid Cycle like this one time then with 10A constant current charge 45min with 15A discharge 24min, back and forth carry out.When battery power discharge voltage is lower than 31.5v, the Rapid Cycle end-of-life, two Battery pack actual detected Rapid Cycle life-spans were respectively 282 times and 290 times, and the normal battery actual detected Rapid Cycle life-span is respectively 255 times and 257 times.
From above-mentioned battery, get in addition 4 groups of test cells in 25 ℃ ± 2 ℃ environment with two groups of normal battery, be discharged to battery pack final pressure 31.5v with constant current 5A, with constant voltage 44.4v, current limliting 1.8A charging 10h, constitute 100%DOD (100% a depth of discharge) life-span to circulate then.When be lower than 84min the discharge time of battery pack, be judged as cycle life and stop.4 groups of test cell 100%DOD (100% depth of discharge) cycle life has been carried out respectively 371 times, 366 times, 372 times, 377 times; Normal battery is respectively 350 times and 341 times.
Claims (1)
1, a kind of lead acid storage battery of electric booster car and cream technique, with the lead powder is primary raw material, successively add additive, pure water, sulfuric acid and make lead plaster, it is characterized in that with the cream process in add suspension and mix, the adding of suspension after adding pure water and stirring 5 minutes with adding sulfuric acid before, to the raw material of every 100kg lead powder, add 3～4L suspension, the proportioning of described suspension is:
Anodal suspension: deionized water 100kg, nano silicon 9.5～10.5kg, aquadag 5～10kg, ptfe emulsion 9.5～10.5kg of 60%;
Negative pole suspension: deionized water 100kg, acetylene black 4.5～5.5kg, lignin 5～6kg, carbon black 14.5～15.5kg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100956730A CN100557863C (en) | 2005-11-24 | 2005-11-24 | Lead-acid storage battery and paste mixing process for electric moped |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100956730A CN100557863C (en) | 2005-11-24 | 2005-11-24 | Lead-acid storage battery and paste mixing process for electric moped |
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| Publication Number | Publication Date |
|---|---|
| CN1971977A CN1971977A (en) | 2007-05-30 |
| CN100557863C true CN100557863C (en) | 2009-11-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2005100956730A Expired - Fee Related CN100557863C (en) | 2005-11-24 | 2005-11-24 | Lead-acid storage battery and paste mixing process for electric moped |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101887971A (en) * | 2010-05-14 | 2010-11-17 | 张天任 | Lead paste formula of energy storing accumulator and preparation method thereof |
| CN101882681A (en) * | 2010-06-21 | 2010-11-10 | 冯家齐 | Positive and negative plate additive of lead-acid accumulator and preparation method thereof |
| CN101958417A (en) * | 2010-07-26 | 2011-01-26 | 武汉银泰科技电源股份有限公司 | Anode additive of lead acid storage battery |
| CN101969149B (en) * | 2010-09-25 | 2012-08-29 | 张天任 | Mixed cathode diachylon of superbattery and preparation method thereof |
| CN102306786A (en) * | 2011-07-15 | 2012-01-04 | 山东圣阳电源股份有限公司 | Positive active substance for high-temperature fixed lead acid battery |
| CN102496723A (en) * | 2011-12-31 | 2012-06-13 | 河南三丽电源股份有限公司 | Storage battery lead paste used for powering electric automobile and preparation method thereof |
| CN103682357A (en) * | 2012-09-24 | 2014-03-26 | 海洋王照明科技股份有限公司 | Graphene composite electrode material and preparation method thereof, lead-carbon battery negative electrode lead plaster and preparation method thereof as well as lead-carbon battery |
| CN103904331A (en) * | 2012-12-31 | 2014-07-02 | 陈荣 | Formula of additive for improving low-temperature charge property of lead-acid storage battery |
| CN103219512B (en) * | 2013-03-25 | 2015-05-13 | 超威电源有限公司 | Deep circulation storage battery container formation diachylon |
| CN105958064A (en) * | 2016-06-15 | 2016-09-21 | 浙江天能动力能源有限公司 | Negative electrode lead paste for battery of low-speed electric vehicle |
| CN109659558A (en) * | 2018-11-16 | 2019-04-19 | 佛山市科特电池有限公司 | A kind of electric road vehicle lead storage battery green plate lead paste formula |
| CN110247053A (en) * | 2019-06-21 | 2019-09-17 | 天能电池(芜湖)有限公司 | A kind of binder for lead carbon battery |
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| CN1337751A (en) * | 2000-08-04 | 2002-02-27 | 舟山明日纳米材料有限公司 | Manufacture of lead accumulator modified by nanometer silicon-base oxide |
| CN1549364A (en) * | 2003-05-07 | 2004-11-24 | 浙江南都电源动力股份有限公司 | Negative pole active material for lead-acid colloid accumulator cell |
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2005
- 2005-11-24 CN CNB2005100956730A patent/CN100557863C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1337751A (en) * | 2000-08-04 | 2002-02-27 | 舟山明日纳米材料有限公司 | Manufacture of lead accumulator modified by nanometer silicon-base oxide |
| CN1549364A (en) * | 2003-05-07 | 2004-11-24 | 浙江南都电源动力股份有限公司 | Negative pole active material for lead-acid colloid accumulator cell |
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| CN1971977A (en) | 2007-05-30 |
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