CN101916861A - Cathode lead plaster capable of prolonging fast charge-discharge circulating life of battery and preparation method thereof - Google Patents
Cathode lead plaster capable of prolonging fast charge-discharge circulating life of battery and preparation method thereof Download PDFInfo
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- CN101916861A CN101916861A CN2010102404656A CN201010240465A CN101916861A CN 101916861 A CN101916861 A CN 101916861A CN 2010102404656 A CN2010102404656 A CN 2010102404656A CN 201010240465 A CN201010240465 A CN 201010240465A CN 101916861 A CN101916861 A CN 101916861A
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a cathode lead plaster capable of prolonging a fast charge-discharge circulating life of a battery and a preparation method thereof, which are used for solving the problem of the fast charge-discharge circulating life of a lead-acid battery in a partial charge state. The lead plaster comprises the following raw materials in part by weight: 100 parts of lead powder, 0.05 to 0.1 part of polyester fiber, 0.5 to 1.0 part of barium sulfate, 0.05 to 0.5 part of lignin sodium sulfonate, 0 to 1.0 part of humic acid and 0.05 to 1.0 part of super-conducting carbon black. In the lead plaster of the invention, the nano-scale super-conducting carbon black is used as an additive of a cathode active substance, so that the sulfation problem of the cathode active substance under the fast charge-discharge circulating condition in the partial charge state is solved, the conductivity and porosity of the cathode active substance are improved, and the charge acceptance of the active substance is improved. Comparison experiments show that the effective circulating times of the lead-acid battery prepared from the cathode lead plaster are multiple times greater than those of the common lead-acid battery, and the circulating life of the battery is obviously prolonged.
Description
Technical field
Type of the present invention relates to a kind of accumulator material and preparation method, particularly improves the shallow cathode lead plaster that charges and discharge cycle life under the lead acid accumulator part state-of-charge, belongs to the battery technology field.
Background technology
Be the protection environment, the Hybrid Vehicle storage battery arises at the historic moment.Hybrid power for shallow under the part state-of-charge charges and discharge circulation, has proposed new requirement to life of storage battery performance with the user mode of lead acid accumulator.Shallow charge and discharge cycles under the part state-of-charge, active material especially negative electrode active material are easy to take place sulfation.Storage battery forms the PbSO of little crystal grain in normal discharge process
4, surface area is very big, and is relatively more active, is easy to change lead in charging process.But this fine polycrystal system has the tendency, the especially storage battery that reduce surface free energy to be in for a long time under the situation of undercharge, on the one hand part PbSO
4Can not in time be converted into lead, on the other hand, PbSO be arranged constantly when discharge
4Deposition is got off, and makes PbSO
4Particle is grown up, and becomes the lead sulfate crystal of the oversize grain that can not normally transform gradually, sulfation occurs.Sulfation has consumed a part of sulfuric acid, has reduced the amount of active material, and thick lead sulfate crystal has also stopped up many passages simultaneously, influence sulfuric acid electrolyte and enter active material inside, blocked the partial reaction area, the internal resistance of cell is enlarged markedly, capacity sharply descends, and causes battery failure.Be easy to cause the negative pole sulfation based on this kind life-span circulation pattern, and battery will bear the requirements such as momentary charge that braking energy reclaims big electric current, therefore the charge acceptance to this type storage battery requires quite high.
Carbon black and acetylene carbon black can improve the conductivity of active material as the negative electrode active material additive that improves charge acceptance, improve the voidage of active material, and can regulate the distribution of surface reactive material or organic expander, help discharging product PbSO
4Dissolving and Pb
2+The reduction crystallization, improve the charge acceptance of electrode.But show through test, add on the basis of ordinary carbon black about 0.2% at normal cathode lead plaster prescription, the addition of carbon black is brought up to 1%, the effect that delays the negative electrode active material sulfation is still not enough, the visible simple requirement that ordinary carbon black content can't satisfy further raising charge acceptance that improves.Battery lost efficacy after circulation more than 10000 time when selecting acetylene carbon black for use, and failure mode is the negative plate sulfation, and poor by charge acceptance, long-term undercharge causes.In sum, adopt the cathode lead plaster of prior art, as the additive that improves charge acceptance, can not satisfy and improve the shallow requirement that charges and discharge cycle life of storage battery with ordinary carbon black and acetylene carbon black.
Summary of the invention
Technical problem to be solved by this invention is the defective that overcomes above-mentioned prior art, provide a kind of and improve the shallow cathode lead plaster that charges and discharge cycle life of storage battery, under the part state-of-charge, have good cycle life in shallow the recycling thereby be used in the hybrid vehicle storage battery.
The alleged problem of the present invention is by solving with following technical proposals:
A kind of shallow cathode lead plaster that charges and discharge cycle life of storage battery that improves, described lead plaster raw material is a following weight unit's matter: lead powder 100, polyester fiber 0.05～0.1, barium sulfate 0.5～1.0, sodium lignosulfonate 0.05～0.5, humic acid 0～1.0, superconduct carbon black 0.05～1.0, described superconduct carbon black is the nanoscale carbon black, and described barium sulfate was the powder-material of 45 μ m sieve apertures, residue on sieve≤0.10%.
The above-mentioned shallow cathode lead plaster that charges and discharge cycle life of storage battery that improves, lead oxide content is 65～85% in the described lead powder.
The above-mentioned shallow cathode lead plaster preparation method who charges and discharge cycle life of storage battery that improves, it is undertaken by following operation:
A. prepare burden: take by weighing each raw material by above-mentioned lead plaster solid material proportioning;
B. do and mix: above-mentioned lead plaster solid material is put into paste mixing machine do mixed;
C. wet mixing: the pure water that takes by weighing raw material weight 10～12% joins in the paste mixing machine, stirs;
D. drench acid: add the 1.400g/cm that raw material weight 4～8%, density are with the spray shape while stirring
3Sulfuric acid solution and cream temperature be lower than below 65 ℃, go out the cream temperature and be lower than 45 ℃.
The present invention is directed to common negative electrode active material additive can't satisfy hybrid power and charge and discharge the problem that cycle life requires with shallow under the lead acid accumulator part state-of-charge, through groping test repeatedly, design a kind of suitable hybrid power with lead-acid accumulator negative pole lead paste and preparation method.Described lead plaster screening nanoscale superconduct carbon black is as the negative electrode active material additive, solve the sulfation problem of negative electrode active material under shallow charge and discharge cycles condition under the part state-of-charge, improve the electricity of negative electrode active material and lead and porosity, improve the charge acceptance of active material.Contrast test shows, effective cycle-index of the lead acid accumulator made from cathode lead plaster of the present invention, the lead acid accumulator of making than common cathode lead plaster exceeds several times, has obviously prolonged the cycle life of storage battery, reaches the instructions for use of hybrid power with lead acid accumulator.
Embodiment
Cathode lead plaster of the present invention aims at and is used for that the shallow cycle life that charges and discharge designs with storage battery under the part state-of-charge, its raw material proportioning is: lead powder 100, polyester fiber 0.05～0.1, barium sulfate 0.5～1.0, sodium lignosulfonate 0.05～0.5, humic acid 0～1.0, superconduct carbon black 0.05～1.0, wherein the superconduct carbon black is nanometer materials, and barium sulfate is pulverulent material (crossing 45 μ m sieve apertures, residue on sieve≤0.10%).Selecting the superconduct carbon black is core technology of the present invention as cathode additive agent and strict control adding proportion.Described superconduct carbon black also claims the high electric conductivity carbon black, it exceeds more than 10 times than carbon black conductivity commonly used, select the superconduct carbon black to substitute carbon black commonly used and join in the negative electrode active material, to improving the charge acceptance of negative plate, the sulfation that delays negative electrode active material has significant effect.The nano-scale particle of superconduct carbon black makes that its distribution in active material is more even, this has just improved the charge acceptance of negative electrode active material greatly, make battery under identical charge condition, can fill into more electric weight, reduced the charging degree of unsaturation of battery, delay the sulfation of negative plate, prolonged the cycle life of storage battery.Test shows, superconduct carbon black addition is very few, be not enough to improve effectively the charge acceptance of negative electrode active material, and addition too much not only makes the negative pole overpotential of hydrogen evolution obviously reduce, and can also cause that anodal charging potential is very high, quickens separating out of oxygen, reduce the oxygen compounding efficiency, the cell water consumption strengthens, and dry too early, the life-span ends.This can draw from the electrode potential analysis of circulation time: anodal charging potential is very high, the negative pole charging potential is very low, though charge volume is improved, but because anodal charging potential height, it is more to make oxygen separate out, cause negative pole to increase the weight of undercharge owing to oxygen reduction reaction, sulfation is quickened.Therefore want the addition of strict control negative electrode active material conductive carbon black, the both positive and negative polarity charging potential is remained on to improve charge volume to be unlikely to oxygen again and separate out too much.
Table 1 is to adopt lead acid accumulator that the different additive cathode lead plaster makes through life-span number of times that test reaches:
Table 1
By table 1 data as can be seen, be that the lead acid accumulator that the cathode lead plaster of active additive is made is compared with the lead acid accumulator of cathode lead plaster prescription commonly used production with the superconduct carbon black, cycle life is significantly improved.
Several instantiations below are provided:
Embodiment 1: with 100kg PbO content is that 65%～85% lead powder adds in the paste mixing machine, add 0.05kg polyester fiber, 0.5kg barium sulfate, 0.1kg sodium lignosulfonate, 0.3kg humic acid, 0.05kg nanoscale superconduct carbon black simultaneously, above-mentioned material is stirred, adding 10kg then purifies waste water, after hygrometric state mixed, drenching density fast was 1.400g/cm
3Control and cream temperature are lower than 65 ℃ in the sulfuric acid solution 4kg of (25 ℃) and the cream process, reaction evenly and temperature drop to below 45 ℃, go out the cream use.
Embodiment 2: with 100kg PbO content is that 65%～85% lead powder adds in the paste mixing machine, add 0.07kg polyester fiber, 0.6kg barium sulfate, 0.3kg sodium lignosulfonate, 0.1kg humic acid, 0.25kg nanoscale superconduct carbon black simultaneously, above-mentioned material is stirred, adding 11kg then purifies waste water, after hygrometric state mixed, drenching density fast was 1.400g/cm
3Control and cream temperature are lower than 65 ℃ in the sulfuric acid solution 6kg of (25 ℃) and the cream process, reaction evenly and temperature drop to below 45 ℃, go out the cream use.
Embodiment 3: with 100kg PbO content is that 65%～85% lead powder adds in the paste mixing machine, add 0.1kg polyester fiber, 1.0kg barium sulfate, 0.5kg sodium lignosulfonate, 1.0kg nanoscale superconduct carbon black simultaneously, above-mentioned material is stirred, adding 12kg then purifies waste water, after hygrometric state mixed, drenching density fast was 1.400g/cm
3Control and cream temperature are lower than 65 ℃ in the sulfuric acid solution 8kg of (25 ℃) and the cream process, reaction evenly and temperature drop to below 45 ℃, go out the cream use.
Embodiment 4: with 100kg PbO content is that 65%～85% lead powder adds in the paste mixing machine, add 0.09kg polyester fiber, 0.7kg barium sulfate, 0.2kg sodium lignosulfonate, 0.08kg nanoscale superconduct carbon black simultaneously, above-mentioned material is stirred, adding 12kg then purifies waste water, after hygrometric state mixed, drenching density fast was 1.400g/cm
3Control and cream temperature are lower than 65 ℃ in the sulfuric acid solution 8kg of (25 ℃) and the cream process, reaction evenly and temperature drop to below 45 ℃, go out the cream use.
Embodiment 5: with 100kg PbO content is that 65%～85% lead powder adds in the paste mixing machine, add 0.06kg polyester fiber, 0.8kg barium sulfate, 0.4kg sodium lignosulfonate, 0.05kg nanoscale superconduct carbon black simultaneously, above-mentioned material is stirred, adding 12kg then purifies waste water, after hygrometric state mixed, drenching density fast was 1.400g/cm
3Control and cream temperature are lower than 65 ℃ in the sulfuric acid solution 8kg of (25 ℃) and the cream process, reaction evenly and temperature drop to below 45 ℃, go out the cream use.
The anode diachylon of preparation as stated above is coated on the grid, solidifies 24h, produce the negative plate of giving birth to through 70 ℃, the dry 24h of 20%RH again, just give birth to plate and can adopt automobile start maintenance free cell anode diachylon and the manufacturing of pole plate manufacture craft through 40 ℃, 98%RH.Behind polar plate solidification, drying, branch plate, use the AGM dividing plate, the private casing of packing into, sealing becomes the automobile start maintenance free cell.
Claims (3)
1. one kind can be improved the shallow cathode lead plaster that charges and discharge cycle life of storage battery, it is characterized in that: described lead plaster raw material is a following weight unit's matter: lead powder 100, polyester fiber 0.05～0.1, barium sulfate 0.5～1.0, sodium lignosulfonate 0.05～0.5, humic acid 0～1.0, superconduct carbon black 0.05～1.0, described superconduct carbon black is the nanoscale carbon black, and described barium sulfate was the powder-material of 45 μ m sieve apertures, residue on sieve≤0.10%.
2. the shallow cathode lead plaster that charges and discharge cycle life of storage battery that improves according to claim 1, it is characterized in that: lead oxide content is 65%～85% in the described lead powder.
3. the shallow cathode lead plaster preparation method who charges and discharge cycle life of storage battery that improves according to claim 1 and 2 is characterized in that it is undertaken by following operation:
A. prepare burden: take by weighing each raw material by above-mentioned lead plaster solid material proportioning;
B. do and mix: above-mentioned lead plaster solid material is put into paste mixing machine do mixed;
C. wet mixing: the pure water that takes by weighing raw material weight 10～12% joins in the paste mixing machine, stirs;
D. drench acid: add the 1.400g/cm that raw material weight 4～8%, density are with the spray shape while stirring
3Sulfuric acid solution and cream temperature be lower than below 65 ℃, go out the cream temperature and be lower than 45 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102404656A CN101916861A (en) | 2010-07-30 | 2010-07-30 | Cathode lead plaster capable of prolonging fast charge-discharge circulating life of battery and preparation method thereof |
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| CN2010102404656A CN101916861A (en) | 2010-07-30 | 2010-07-30 | Cathode lead plaster capable of prolonging fast charge-discharge circulating life of battery and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102074703A (en) * | 2010-12-28 | 2011-05-25 | 株洲冶炼集团股份有限公司 | Negative pole lead paste for lead-carbon super storage battery and preparation method thereof |
| CN103163473A (en) * | 2012-12-27 | 2013-06-19 | 惠州市亿能电子有限公司 | Method of testing circulation durability of energy storage system storage battery |
| CN103413946A (en) * | 2013-07-12 | 2013-11-27 | 超威电源有限公司 | Formula of lead-acid storage battery negative pole diachylon |
| CN105355915A (en) * | 2015-11-24 | 2016-02-24 | 江苏华富储能新技术股份有限公司 | Lead accumulator cathode lead paste containing superconducting material additive |
| CN105355914A (en) * | 2015-11-24 | 2016-02-24 | 江苏华富储能新技术股份有限公司 | Preparation method of lead accumulator anode lead paste containing superconducting material additive |
| CN105355913A (en) * | 2015-11-24 | 2016-02-24 | 江苏华富储能新技术股份有限公司 | High-efficiency lead accumulator anode lead paste containing superconducting material additive |
| CN105375025A (en) * | 2015-11-24 | 2016-03-02 | 江苏华富储能新技术股份有限公司 | Lead storage battery positive electrode lead paste containing superconducting material additive |
| CN105375024A (en) * | 2015-11-24 | 2016-03-02 | 江苏华富储能新技术股份有限公司 | Preparation method of lead storage battery cathode lead paste containing superconducting material additive |
| CN105390668A (en) * | 2015-11-24 | 2016-03-09 | 江苏华富储能新技术股份有限公司 | Lead storage battery containing superconducting material additive |
| CN105428601A (en) * | 2015-11-24 | 2016-03-23 | 江苏华富储能新技术股份有限公司 | Preparation method of lead-storage-battery cathode lead plaster containing superconducting material additive |
| CN105449219A (en) * | 2015-11-24 | 2016-03-30 | 江苏华富储能新技术股份有限公司 | High-efficiency lead storage battery anode lead paste containing superconducting material additive |
| CN105470502A (en) * | 2015-11-24 | 2016-04-06 | 江苏华富储能新技术股份有限公司 | Positive lead plaster containing superconducting material additive for lead storage battery |
| CN111600018A (en) * | 2019-10-23 | 2020-08-28 | 骆驼集团蓄电池研究院有限公司 | Negative lead paste suitable for high-temperature and low-temperature environments, lead-acid storage battery and preparation method |
| CN112786843A (en) * | 2021-02-02 | 2021-05-11 | 天能电池集团股份有限公司 | Low-temperature lead storage battery negative electrode lead paste and negative plate |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102074703A (en) * | 2010-12-28 | 2011-05-25 | 株洲冶炼集团股份有限公司 | Negative pole lead paste for lead-carbon super storage battery and preparation method thereof |
| CN102074703B (en) * | 2010-12-28 | 2012-11-07 | 株洲冶炼集团股份有限公司 | Negative pole lead paste for lead-carbon super storage battery and preparation method thereof |
| CN103163473A (en) * | 2012-12-27 | 2013-06-19 | 惠州市亿能电子有限公司 | Method of testing circulation durability of energy storage system storage battery |
| CN103413946A (en) * | 2013-07-12 | 2013-11-27 | 超威电源有限公司 | Formula of lead-acid storage battery negative pole diachylon |
| CN105355915A (en) * | 2015-11-24 | 2016-02-24 | 江苏华富储能新技术股份有限公司 | Lead accumulator cathode lead paste containing superconducting material additive |
| CN105355914A (en) * | 2015-11-24 | 2016-02-24 | 江苏华富储能新技术股份有限公司 | Preparation method of lead accumulator anode lead paste containing superconducting material additive |
| CN105355913A (en) * | 2015-11-24 | 2016-02-24 | 江苏华富储能新技术股份有限公司 | High-efficiency lead accumulator anode lead paste containing superconducting material additive |
| CN105375025A (en) * | 2015-11-24 | 2016-03-02 | 江苏华富储能新技术股份有限公司 | Lead storage battery positive electrode lead paste containing superconducting material additive |
| CN105375024A (en) * | 2015-11-24 | 2016-03-02 | 江苏华富储能新技术股份有限公司 | Preparation method of lead storage battery cathode lead paste containing superconducting material additive |
| CN105390668A (en) * | 2015-11-24 | 2016-03-09 | 江苏华富储能新技术股份有限公司 | Lead storage battery containing superconducting material additive |
| CN105428601A (en) * | 2015-11-24 | 2016-03-23 | 江苏华富储能新技术股份有限公司 | Preparation method of lead-storage-battery cathode lead plaster containing superconducting material additive |
| CN105449219A (en) * | 2015-11-24 | 2016-03-30 | 江苏华富储能新技术股份有限公司 | High-efficiency lead storage battery anode lead paste containing superconducting material additive |
| CN105470502A (en) * | 2015-11-24 | 2016-04-06 | 江苏华富储能新技术股份有限公司 | Positive lead plaster containing superconducting material additive for lead storage battery |
| CN111600018A (en) * | 2019-10-23 | 2020-08-28 | 骆驼集团蓄电池研究院有限公司 | Negative lead paste suitable for high-temperature and low-temperature environments, lead-acid storage battery and preparation method |
| CN112786843A (en) * | 2021-02-02 | 2021-05-11 | 天能电池集团股份有限公司 | Low-temperature lead storage battery negative electrode lead paste and negative plate |
| CN112786843B (en) * | 2021-02-02 | 2022-05-17 | 天能电池集团股份有限公司 | Low-temperature lead storage battery negative electrode lead paste and negative plate |
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Application publication date: 20101215 |