CN101969149A - Mixed cathode diachylon of superbattery and preparation method thereof - Google Patents
Mixed cathode diachylon of superbattery and preparation method thereof Download PDFInfo
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- CN101969149A CN101969149A CN2010102907180A CN201010290718A CN101969149A CN 101969149 A CN101969149 A CN 101969149A CN 2010102907180 A CN2010102907180 A CN 2010102907180A CN 201010290718 A CN201010290718 A CN 201010290718A CN 101969149 A CN101969149 A CN 101969149A
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Abstract
The invention discloses mixed cathode diachylon of a superbattery and a preparation method thereof. The diachylon is prepared by mixing the following raw materials in parts by weight: 100 parts of lead powder, 4-10 parts of sulfuric acid, 0.1-8 parts of organic binder, 0.1-2 parts of barium sulfate, 0.01-2 parts of hydrogen separating inhibitor, 1-7 parts of active carbon, 0.1-3 parts of heterodromous graphite, 0.05-1 part of acetylene black, 1-4 parts of humic acid, 5-15 parts of red lead, 12-21 parts of water and 0.1-0.2 part of short fiber. By adding the hydrogen separating inhibitor, the active carbon maintains high-performance capacitance characteristics, so that an electrode has high capacitance. In a part of charge state, the recycling service life of the superbattery is improved by more than 10 times compared with a common lead-acid storage battery.
Description
Technical field
The present invention relates to the lead acid accumulator preparation field, be specifically related to the superbattery cathode lead plaster.
Background technology
Lead acid accumulator is in daily use, because using method is improper or the charging environment can't satisfy the operating state of the condition of battery, particularly hybrid-power battery, longly makes battery owe to fill shallow putting, and causes battery lost efficacy (PCL3) to occur at last.
For solving this technical problem, current lead acid accumulator industry develops innovatively ultracapacitor is combined with the existing storage battery advantage, and the high-power characteristic of ultracapacitor and storage battery high-energy-density characteristic are embodied a concentrated reflection of.Super capacitance storage battery is disclosed as patent application 2009102098751, this patent application has added the graininess capacitance electrode material and has made the combined type negative plate in the negative plate lead plaster of common lead acid accumulator, described capacitance electrode material is made up of material with carbon element, conductive agent, binding agent, material with carbon element wherein is the active carbon carbon nano-tube ... in one or more, conductive agent wherein is carbon black, acetylene black, graphite ... in one or more, binding agent wherein is one or more mixtures in PTFE/PVDF/CMC/ fluorubber and the neoprene.But capacitance electrode material to be made graininess in its preparation, complicated process of preparation not only, and may cause and can't mix.Simultaneously, do not add the liberation of hydrogen inhibitor in lead plaster, the charcoal of adding can't be brought into play the characteristic of due super capacitor, can't guarantee that promptly ultracapacitor discharges and recharges earlier in charge and discharge process, shields to battery.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of superbattery mixing cathode lead plaster, the battery made from the negative plate of this lead paste formula, have superior high rate during charging-discharging, excellent recycle the life-span, and charge acceptance is strong, cryogenic property is good.Another technical problem that the present invention will solve provides the preparation method of this lead paste formula.
The present invention is achieved through the following technical solutions:
Superbattery mixing cathode lead plaster is mixed by following raw materials in weight portion: lead powder: 100, and sulfuric acid: 4～10, binding agent: 0.1～8, barium sulfate: 0.1～2, the liberation of hydrogen inhibitor: 0.01～2, active carbon 1～7, incorgruous graphite 0.1～3, acetylene black 0.05～1, humic acid: 1～4, red lead: 5～15, water: 12～21, short fiber: 0.1～0.2.
Binding agent in the superbattery mixing cathode lead plaster is mixed organic additive by following raw materials in weight portion: ethylene-vinyl acetate copolymer (EVA): polyvinyl alcohol: water :=1: 0.1～0.8: 1～3: 15～20.
Organic additive described in the binding agent is that polytetrafluoroethylene (PTFE), butadiene-styrene rubber, CMC are a kind of or two kinds or two or more mixing in the sodium carboxymethylcellulose.
Liberation of hydrogen inhibitor described in the lead plaster is a kind of or two kinds or the two or more mixing in indium oxide, bismuth oxide, stearic acid or the barium stearate.
The preparation method of superbattery mixing cathode lead plaster comprises the following steps:
(1) by above-mentioned weight portion proportioning, lead powder, barium sulfate, liberation of hydrogen inhibitor, active carbon, incorgruous graphite, acetylene black, red lead, humic acid, short fiber weighing are poured in the container, stir 5-10min, each component is fully mixed;
(2) by above-mentioned weight portion proportioning, water is added in step (1) container fast, add the back and continue to stir 5-10min; This step adds water, needs to add fast, and the general control time finished in 1-2 minute;
(3) by above-mentioned weight portion proportioning, sulfuric acid is slowly added in step (2) container in the time at 8-15min, the control temperature is lower than 70 ℃ in adition process, adds the back and continues to stir 5-10min;
(4) by above-mentioned weight portion proportioning, in the container of step (3), add binding agent, add the back and continue to stir 5-10min, control lead plaster apparent density is at 3.8-4.5g/ml.
Adopt conventional lead-acid battery to produce the smear facility condition, just above-mentioned lead plaster can be coated onto on the negative electrode grid, the pole plate that makes after solidifying has extraordinary appearance characteristics and excellent battery electrical property.
Out-phase graphite significant feature is a conduction, because after adding adhesive, the internal resistance of battery generally can increase.And graphite belongs to the charcoal class, and itself also has capacitance characteristic.Out-phase graphite and common graphite difference are that its hydrogen-evolution overpotential is low than the hydrogen-evolution overpotential of common graphite.
Indium oxide or bismuth oxide and stearic acid, barium stearate are good liberation of hydrogen inhibitor, it mainly is the liberation of hydrogen that reduces battery, the affiliation that adds of charcoal makes battery shift to an earlier date liberation of hydrogen, because if the hydrogen-evolution overpotential of charcoal is equal to or a little less than the hydrogen-evolution overpotential of lead, the performance that could guarantee electric capacity is brought into play like this, and promptly in charge and discharge process, electric capacity at first discharges and recharges, thereby battery is played cushioning effect, extending battery life.The liberation of hydrogen inhibitor is core technology, the key point of superbattery.
The negative plate that lead plaster of the present invention is made is formed battery with the positive plate that conventional lead plaster is made, and has battery and capacitance characteristic, compared with prior art, has the following advantages:
One, the present invention is because process granulation processing of the material with carbon element that adds, more owing to be added with the liberation of hydrogen inhibitor, active carbon has wherein kept high performance capacitance characteristic, makes electrode possess high electric capacity, brings up to 300～400F/g by present known 200～300F/g.
Two, binding agent of the present invention greatly strengthens other material adhesions in material with carbon element (active carbon, incorgruous graphite, acetylene black) and the lead plaster, outward appearance is closely knit behind the polar plate solidification, can the conventional pole plate of strength ratio be improved (use data declaration), improved the charge acceptance of battery simultaneously.(be about to pole plate and place certain altitude through drop test, allow it fall naturally, the drop number when lead plaster partially or completely comes off), the corrosion situation of observing grid simultaneously, more than the drop number of common batteries pole plate, corrosion condition also is better than common batteries to the drop number of super battery plate slightly.Because cohesive force is strong, makes battery not analyse, not ooze charcoal in charge and discharge process, the superbattery of being assembled has excellent cycle life.
Three, You Yi cycle life.Owing to be added with the liberation of hydrogen inhibitor, in charge and discharge process, can guarantee that electric capacity at first discharges and recharges, thereby battery is shielded.Under the part state-of-charge, the cycle life of superbattery improves more than 10 times than common lead acid accumulator.
Four, high rate during charging-discharging significantly is better than the common lead acid accumulator.Super accumulator can discharge by 10C, and prior art can only be discharged by 2C; Can charge into more than 90% at 3-4 hour at super accumulator on the charging performance, and prior art charges into more than 90% and to need 10-12 consuming time hour.
Five, charge acceptance is strong.Compare with the common lead acid accumulator, the charge acceptance 4.5-6A of superbattery of the present invention, and the charge acceptance of common lead-acid battery has only 2.0-3.0A.
Six, cryogenic property is good.Discharge and recharge under-15 ℃ of conditions, the performance of superbattery is excellent and common lead acid accumulator obviously.
Embodiment
Embodiment 1
It is standby at first to prepare binding agent.Getting EVA by weight is 5 parts of ethylene-vinyl acetate copolymers, 15 parts of polyvinyl alcohol, and water is put into container for 170 parts, and heat temperature raising to 60～70 ℃, then, getting PTFE is that 10 parts of polytetrafluoroethylene add in the said vesse, adopts about magnetic agitation or ultrasonic dispersion 15min to get final product.
The preparation cathode lead plaster is got 100 parts in lead powder, 10 parts in sulfuric acid, 2 parts of binding agents, 0.8 part in barium sulfate, 0.8 part of indium oxide, 0.8 part of stearic acid, 5 parts of active carbons, 1 part in incorgruous graphite, 0.8 part of acetylene black, 1 part of humic acid, 10 parts of red lead, 15 parts in water, 0.1 part on short fiber by weight.
Its preparation follows these steps to carry out:
(1) lead powder, barium sulfate, indium oxide, stearic acid, active carbon, incorgruous graphite, acetylene black, red lead, humic acid, short fiber are poured in the container, stirred 5-10min, each component is fully mixed;
(2) water is added fast in step (1) container, add the back and continue to stir 5-10min;
(3) sulfuric acid is slowly added in step (2) container in the time at 8-15min, the control temperature is lower than 70 ℃ in adition process, adds the back and continues to stir 5-10min;
(4) add the above-mentioned binding agent that has prepared in the container of step (3), add the back and continue to stir 5-10min, control lead plaster apparent density is at 3.8-4.5g/ml.
Be applied to above-mentioned lead plaster on the negative electrode grid according to a conventional method, under 60 ℃, relative humidity 96% condition, solidify after smear is finished, be no less than 50h curing time, with the negative plate that solidifies and the positive plate that the scribbles common lead plaster battery case of packing into, make the battery of electric vehicle of 6-DZM-12Ah, be internalized into.
In the present embodiment, described sulfuric acid density is 1.40g/ml, and short fiber is the short fiber of battery special use, and its length is 2-4mm.
Battery capacity, charging are accepted, cryogenic property is tested by national standard method, and the cycle life method of testing is that 2.7A charges to 12.5V under the part state-of-charge, and 6A is discharged to 11.8V.
After tested: this battery discharges under the 150A electric current, and specific power reaches more than the 500W/Kg.
Under the part state-of-charge, cycle life reaches more than 100,000 times.
Charging is accepted to reach more than the 5.0A.
Discharge capacity reaches more than the 9.5Ah under-15 ℃ of conditions.
Embodiment 2
Get 100 parts in lead powder, 10 parts in sulfuric acid, 4 parts of binding agents, 0.8 part in barium sulfate, 0.5 part of indium oxide, 0.6 part of stearic acid, 4 parts of active carbons, 1 part in incorgruous graphite, 0.8 part of acetylene black, 1 part of humic acid, 8 parts of red lead, 15 parts in water, 0.1 part on short fiber by weight.
All the other are implemented as embodiment 1.
Embodiment 3
Get 100 parts in lead powder, 9 parts in sulfuric acid, 2.5 parts of binding agents, 1.1 parts in barium sulfate, 0.6 part of bismuth oxide, 0.5 part of barium stearate, 5.5 parts of active carbons, 1.5 parts in incorgruous graphite, 0.6 part of acetylene black, 1.5 parts of humic acids, 9 parts of red lead, 14 parts in water, 0.2 part on short fiber by weight.
All the other are implemented as embodiment 1.
Embodiment 4
Get 100 parts in lead powder, 8 parts in sulfuric acid, 3 parts of binding agents, 1 part in barium sulfate, 0.4 part of indium oxide, 0.8 part of stearic barium, 6 parts of active carbons, 2 parts in incorgruous graphite, 0.7 part of acetylene black, 2 parts of humic acids, 11 parts of red lead, 17 parts in water, 0.15 part on short fiber by weight.
All the other are implemented as embodiment 1.
Claims (5)
1. superbattery mixing cathode lead plaster is characterized in that being mixed by following raw materials in weight portion:
Lead powder: 100, sulfuric acid: 4～10, binding agent: 0.1～8, barium sulfate: 0.1～2, the liberation of hydrogen inhibitor: 0.01～2, active carbon: 1～7, incorgruous graphite: 0.1～3, acetylene black: 0.05～1, humic acid: 1～4, red lead: 5～15, water: 12～21, short fiber: 0.1～0.2%.
2. superbattery mixing cathode lead plaster as claimed in claim 1 is characterized in that: described liberation of hydrogen inhibitor is a kind of or two kinds or the two or more mixing in indium oxide, bismuth oxide, stearic acid or the barium stearate.
3. superbattery mixing cathode lead plaster as claimed in claim 1, it is characterized in that: described binding agent is mixed by following raw materials in weight portion: organic additive: ethylene-vinyl acetate copolymer: polyvinyl alcohol: water=1: 0.1～0.8: 1～3: 15～20.
4. the binding agent in the superbattery mixing cathode lead plaster as claimed in claim 3 is characterized in that: organic additive is a kind of or two kinds or the two or more mixing in polytetrafluoroethylene, butadiene-styrene rubber, the sodium carboxymethylcellulose.
5. prepare the method for the described superbattery mixing of claim 1 cathode lead plaster, it is characterized in that comprising the following steps:
(1) by above-mentioned weight portion proportioning, lead powder, barium sulfate, liberation of hydrogen inhibitor, active carbon, incorgruous graphite, acetylene black, red lead, humic acid, short fiber weighing are poured in the container, stir 5-10min, each component is fully mixed;
(2) by above-mentioned weight portion proportioning, water is added in step (1) container fast, add the back and continue to stir 5-10min;
(3) by above-mentioned weight portion proportioning, sulfuric acid is slowly added in step (2) container in the time at 8-15min, the control temperature is lower than 70 ℃ in adition process, adds the back and continues to stir 5-10min;
(4) by above-mentioned weight portion proportioning, in the container of step (3), add binding agent, add the back and continue to stir 5-10min, control lead plaster apparent density is at 3.8-4.5g/ml.
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| CN2010102907180A CN101969149B (en) | 2010-09-25 | 2010-09-25 | Mixed cathode diachylon of superbattery and preparation method thereof |
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| CN102244249A (en) * | 2011-06-01 | 2011-11-16 | 哈尔滨工业大学 | Carbon-based composite electrode material for super lead-acid battery and preparation method thereof |
| CN102306784A (en) * | 2011-06-29 | 2012-01-04 | 哈尔滨工业大学 | Modified activated carbon with high hydrogen evolution potential and preparation method thereof as well as lead-acid battery negative lead paste containing modified activated carbon |
| CN102709526A (en) * | 2012-06-18 | 2012-10-03 | 奇瑞汽车股份有限公司 | Negative lead plaster of lead-carbon battery and preparation method thereof, negative polar plate and lead-carbon battery |
| CN102709567A (en) * | 2012-06-18 | 2012-10-03 | 奇瑞汽车股份有限公司 | Lead-acid cell |
| CN102738467A (en) * | 2012-06-25 | 2012-10-17 | 天能集团江苏科技有限公司 | Lead-carbon battery anode lead paste for hybrid vehicle, and its preparation method |
| CN102738540A (en) * | 2012-06-25 | 2012-10-17 | 天能集团江苏科技有限公司 | Super battery carbon supplementing method |
| CN102760867A (en) * | 2012-07-25 | 2012-10-31 | 哈尔滨工业大学 | Superbattery polar plate containing grapheme-based hydrogel, preparation method thereof and lead acid superbattery assembled thereby |
| CN102760868A (en) * | 2012-07-25 | 2012-10-31 | 哈尔滨工业大学 | Superbattery polar plate containing vacuum puffed grapheme, preparation method thereof and lead acid superbattery assembled thereby |
| CN102881867A (en) * | 2012-09-29 | 2013-01-16 | 浙江南都电源动力股份有限公司 | Lead carbon mixed negative lead paste and preparation method thereof |
| CN102903895A (en) * | 2011-03-18 | 2013-01-30 | 哈尔滨工业大学 | Electrode material for super lead acid battery, preparation method of electrode material and method for preparing cathode of super lead acid battery by using electrode material |
| CN102931410A (en) * | 2012-10-24 | 2013-02-13 | 超威电源有限公司 | High-capacity formation lead paste and preparation method thereof |
| CN103531791A (en) * | 2013-10-29 | 2014-01-22 | 上饶市云龙实业有限公司 | Super-capacitor lead carbon battery and preparation method thereof |
| CN103579629A (en) * | 2013-11-01 | 2014-02-12 | 双登集团股份有限公司 | Positive pole lead paste of lead-acid storage battery 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 |
| CN103762357A (en) * | 2013-12-30 | 2014-04-30 | 华为技术有限公司 | Lead-acid battery |
| CN103811763A (en) * | 2012-11-13 | 2014-05-21 | 海洋王照明科技股份有限公司 | Graphene-bismuth oxide composite material as well as preparation method thereof, lead carbon battery cathode diachylon as well as preparation method thereof and lead carbon battery cathode plate |
| CN113991110A (en) * | 2021-09-06 | 2022-01-28 | 安徽理士电源技术有限公司 | Negative electrode formula for improving high-temperature performance of lead-acid storage battery and preparation method thereof |
| CN114005979A (en) * | 2021-09-29 | 2022-02-01 | 江苏同科蓄电池股份有限公司 | Negative pole lead paste of power lead-acid storage battery and preparation method thereof |
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| CN102903895B (en) * | 2011-03-18 | 2014-11-12 | 哈尔滨工业大学 | Electrode material for super lead acid battery, preparation method of electrode material and method for preparing cathode of super lead acid battery by using electrode material |
| CN102903895A (en) * | 2011-03-18 | 2013-01-30 | 哈尔滨工业大学 | Electrode material for super lead acid battery, preparation method of electrode material and method for preparing cathode of super lead acid battery by using electrode material |
| CN102244249B (en) * | 2011-06-01 | 2013-06-26 | 哈尔滨工业大学 | Carbon-based composite electrode material for super lead-acid battery and preparation method thereof |
| CN102244249A (en) * | 2011-06-01 | 2011-11-16 | 哈尔滨工业大学 | Carbon-based composite electrode material for super lead-acid battery and preparation method thereof |
| CN102306784A (en) * | 2011-06-29 | 2012-01-04 | 哈尔滨工业大学 | Modified activated carbon with high hydrogen evolution potential and preparation method thereof as well as lead-acid battery negative lead paste containing modified activated carbon |
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| CN102709567A (en) * | 2012-06-18 | 2012-10-03 | 奇瑞汽车股份有限公司 | Lead-acid cell |
| CN102709526B (en) * | 2012-06-18 | 2015-06-10 | 奇瑞汽车股份有限公司 | Negative lead plaster of lead-carbon battery and preparation method thereof, negative polar plate and lead-carbon battery |
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| CN102760867A (en) * | 2012-07-25 | 2012-10-31 | 哈尔滨工业大学 | Superbattery polar plate containing grapheme-based hydrogel, preparation method thereof and lead acid superbattery assembled thereby |
| CN102760867B (en) * | 2012-07-25 | 2014-09-10 | 哈尔滨工业大学 | Superbattery polar plate containing grapheme-based hydrogel, preparation method thereof and lead acid superbattery assembled thereby |
| CN102760868A (en) * | 2012-07-25 | 2012-10-31 | 哈尔滨工业大学 | Superbattery polar plate containing vacuum puffed grapheme, preparation method thereof and lead acid superbattery assembled thereby |
| 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 |
| CN102881867A (en) * | 2012-09-29 | 2013-01-16 | 浙江南都电源动力股份有限公司 | Lead carbon mixed negative lead paste and preparation method thereof |
| CN102881867B (en) * | 2012-09-29 | 2015-07-08 | 浙江南都电源动力股份有限公司 | Lead carbon mixed negative lead paste and preparation method thereof |
| CN102931410A (en) * | 2012-10-24 | 2013-02-13 | 超威电源有限公司 | High-capacity formation lead paste and preparation method thereof |
| CN103811763A (en) * | 2012-11-13 | 2014-05-21 | 海洋王照明科技股份有限公司 | Graphene-bismuth oxide composite material as well as preparation method thereof, lead carbon battery cathode diachylon as well as preparation method thereof and lead carbon battery cathode plate |
| CN103531791A (en) * | 2013-10-29 | 2014-01-22 | 上饶市云龙实业有限公司 | Super-capacitor lead carbon battery and preparation method thereof |
| CN103579629A (en) * | 2013-11-01 | 2014-02-12 | 双登集团股份有限公司 | Positive pole lead paste of lead-acid storage battery and preparation method thereof |
| CN103762357A (en) * | 2013-12-30 | 2014-04-30 | 华为技术有限公司 | Lead-acid battery |
| CN113991110A (en) * | 2021-09-06 | 2022-01-28 | 安徽理士电源技术有限公司 | Negative electrode formula for improving high-temperature performance of lead-acid storage battery and preparation method thereof |
| CN114005979A (en) * | 2021-09-29 | 2022-02-01 | 江苏同科蓄电池股份有限公司 | Negative pole lead paste of power lead-acid storage battery and preparation method thereof |
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Effective date of registration: 20190523 Address after: No. 1 Tianneng Road, Shuyang Economic Development Zone, Suqian City, Jiangsu Province Co-patentee after: Zhejiang Tianneng Battery (Jiangsu) New Energy Co., Ltd. Patentee after: Zhejiang Tianneng Battery (Jiangsu) Co., Ltd. Co-patentee after: Tianneng Group Jiangsu Technology Co.,Ltd. Co-patentee after: Tianneng Group Jiangsu Special Power Supply Co., Ltd. Address before: 223600 No. 1 Tianneng Road, Shuyang County Industrial Park, Suqian, Jiangsu Patentee before: Zhang Tianren |