CN1767237A - Lead-acid accumulator cathode diachylon capable of improving low temperature performance and preparing method - Google Patents
Lead-acid accumulator cathode diachylon capable of improving low temperature performance and preparing method Download PDFInfo
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- CN1767237A CN1767237A CNA2005100148156A CN200510014815A CN1767237A CN 1767237 A CN1767237 A CN 1767237A CN A2005100148156 A CNA2005100148156 A CN A2005100148156A CN 200510014815 A CN200510014815 A CN 200510014815A CN 1767237 A CN1767237 A CN 1767237A
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- lead
- acid accumulator
- negative pole
- cryogenic property
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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
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Abstract
The invention relates to a lead-acid accumulator which can elevate cryogenic property and it's preparing method. The lead plaster solid raw material is formed by (by weight unit) graphite 100, fabric 0.055-0.065, carbon black 0.25-0.35, barium sulfate 0.65-0.75, diversity NNO 0.55-1.5, lignin sodium sulfate 0.05-0.07. It adopts the diversity NNO to replace part of the lignin sodium sulfate, which reduces the effect of the cryogenic start property to the cell after the dissolving of lignin sodium sulfate; it uses test to ascertain the adding range of the diversity.
Description
Technical field
Type of the present invention relates to the used cathode lead plaster of a kind of accumulator material and preparation method, particularly maintenance-free lead accumulator, belongs to the battery technology field.
Background technology
Along with the develop rapidly of auto industry, more and more higher to the performance requirement of lead acid accumulator, the particularly requirement of cold starting performance.According to DIN and IN standard, the discharge time of storage battery when rated current discharges should be greater than 133 seconds, and require twice low temperature discharge all greater than 133 seconds.The common low temperature discharge time for the first time of conventional accumulators is easier to reach, but therefore the low temperature discharge time do not reach standard-required often less than 133 seconds for the second time.When maintenance-free lead accumulator was produced, the cathode lead plaster prescription was at present: lead powder, barium sulfate, carbon black, sodium lignosulfonate, fiber, dilute sulfuric acid and water.Through analysis of experiments, the basic reason that above-mentioned prescription does not reach standard-required in the low temperature discharge time second time is, carrying out along with the storage battery circulation, there is the phenomenon of separating out, dissolving in sodium lignosulfonate from negative electrode active material when charging, and lignosulphonic acid is received separate out, dissolve will cause the electric decreased performance of negative pole, its the most direct performance is that cryogenic property descends, and serious the caused low temperature discharge time does not reach standard-required.According to above analysis, consider to need the prescription of a kind of cathode lead plaster of redesign, the influencing factor of sodium lignosulfonate is reduced, play performance in the hope of improving battery low temperature, satisfy the requirement of automobile factory.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective of above-mentioned prior art and a kind of lead-acid accumulator negative pole lead paste and preparation method who improves cryogenic property is provided, and adopts the maintenance-free lead-acid battery of this method manufacturing to have good cold starting performance and better cycle life thereby make.
The alleged problem of the present invention is solved by following technical scheme:
A kind of lead-acid accumulator negative pole lead paste that improves cryogenic property, its special feature is: the solid material of described lead plaster is made up of following weight unit's matter: lead powder 100, fiber 0.055～0.065, carbon black 0.25～0.35, barium sulfate 0.65～0.75, dispersing agent NNO 0.55～1.5, sodium lignosulfonate 0.05～0.07.
The above-mentioned lead-acid accumulator negative pole lead paste that improves cryogenic property, described dispersing agent NNO content is 0.8～1.2.
The above-mentioned lead-acid accumulator negative pole lead paste that improves cryogenic property, PbO content is 73-84% in the described lead powder.
The above-mentioned preparation method who improves the lead-acid accumulator negative pole lead paste of cryogenic property, it is undertaken by following operation:
A. prepare burden: take by weighing each raw material by above-mentioned lead plaster solid material proportioning;
B. and cream: the pure water that adds raw material weight 10～13% stirs;
C. drench acid: add the sulfuric acid solution of raw material weight 9～10% while stirring with the spray shape, sulfuric acid solution density is 1.40g/cm
3
Lead plaster of the present invention is at the problem of existing maintenance-free lead accumulator low-temperature startup performance difference, change the cathode lead plaster prescription, dispersing agent NNO with doses replaces the part sodium lignosulfonate, thereby reduced sodium lignosulfonate dissolving when charging, separated out the influence of back, and determined the optimum addition range of diffusant by test the battery cold starting performance.Test data shows, adopts the storage battery low temperature discharge time second time of our bright prescription manufacturing obviously to prolong, and can reach standard-required fully, and the capacity of battery also can be up to standard, and cycle life increases to some extent.Its performance index can satisfy the requirement of user vehicle.
Embodiment
The bright cathode lead plaster of we partly substitutes sodium lignosulfonate with diffusant, (have another name called: methylene two how sodium sulfonate) anodized stability is better than sodium lignosulfonate because dispersing agent NNO, therefore reduced sodium lignosulfonate dissolving when charging, separated out the influence degree of back to the battery cold starting performance, the low temperature discharge time obviously increases for the second time to make storage battery.The results showed, if the addition of dispersing agent NNO less than 0.55% poor performance at low temperatures when (degree calculates with the lead powder weight ratio, down with), and if be higher than at 1.5% o'clock and the cream technique poor performance, and cryogenic property has downward trend.
The battery of tests data are provided below: prescription sees Table 1, and result of the test sees Table 2.
Table 1 cathode formula
| Sodium lignosulfonate addition (%) | Dispersing agent NNO (%) | The battery numbering |
| 0.25 | 0 | A battery (original formulation) |
| 0.05～0.07 | 0.55 | B battery |
| 0.8 | The C battery | |
| 1.0 | The D battery | |
| 1.2 | The E battery | |
| 1.5 | The F battery |
Table 2 battery testing result
| Sequence number | Test event | Index request | A | B | C | D | E | F |
| 1 | 20h leads capacity (Ah) | ≥60 | 62.5 | 61.0 | 61.5 | 62.3 | 62.6 | 62.4 |
| 2 | The cold-starting time (s) first time | ≥133 | 155 | 133 | 145 | 160 | 158 | 139 |
| 3 | 20h leads capacity (Ah) | ≥60 | 62.8 | 61.4 | 61.7 | 62.6 | 62.7 | 62.6 |
| 4 | The cold-starting time (s) second time | ≥133 | 130 | 134 | 140 | 149 | 148 | 135 |
| 5 | Cycle life (inferior) | ≥120 | 129 | 125 | 130 | 150 | 151 | 130 |
Experimental condition: 20h leads capacity test, with 3.0A discharge, final voltage 10.5V;-18 ℃ of cold-start tests with 480A discharge 10s, are stopped 10s, then are discharged to 6.0V with 280A again; Cycling life test is in 40 ℃ water-bath, 1. with the 15A 2h that discharges; 2. use constant voltage 16V, the current limliting 15A 5h that charges; Above-mentionedly 1., 2. constitute a circulation, when discharge voltage during less than 10.0V, end-of-life.
By table 2 data as can be seen, add diffusant after, it is more approaching that B, C, D, E, F battery 20h lead the battery A of capacity and original formulation, and all reach capacity requirement; When twice-18 ℃ of cold-starting discharged, originally the low temperature discharge time second time of prescription A battery does not reach requirement, adopt B, C, D, E, twice cold-starting of F battery of new prescription all to reach requirement, and lower B battery of diffusant content and higher F battery for the second time the low temperature discharge time near the critical value of standard-required.In cycling life test, the cycle life of other battery all is higher than the A battery of original formulation except that B battery.Above-mentioned test data can be confirmed: the dispersing agent NNO with suitable dose partly replaces sodium lignosulfonate, can effectively improve storage battery cold starting performance and cycle life, and the addition optimum range of dispersing agent NNO is 0.8%～1.2%.
Several embodiment below are provided:
Example 1: the PbO of 50kg73%～85% is added in the paste mixing machine, the fiber, 0.15kg carbon black, the barium sulfate of 0.35kg, the sodium lignosulfonate of 0.03kg, the dispersing agent NNO of 0.275kg that add 0.03kg simultaneously, and above-mentioned additive stirred, add purifying waste water of 6kg then, adding density at last is 1.400g/cm
3The sulfuric acid 4.9kg of (25 ℃), limit edged stir and the cream process in should control with the cream temperature less than 65 ℃, go out the cream temperature at 30 ℃～45 ℃.
Example 2: the PbO of 50kg73%～85% is added in the paste mixing machine, the fiber, 0.125kg carbon black, the barium sulfate of 0.325kg, the sodium lignosulfonate of 0.025kg, the dispersing agent NNO of 0.4kg that add 0.0275kg simultaneously, and above-mentioned additive stirred, add purifying waste water of 5kg then, adding density at last is 1.400g/cm
3The sulfuric acid 4.5kg of (25 ℃), limit edged stir and the cream process in should control with the cream temperature less than 65 ℃, go out the cream temperature at 30 ℃～45 ℃.
Example 3: the PbO of 50kg73%～85% is added in the paste mixing machine, the fiber, 0.175kg carbon black, the barium sulfate of 0.375kg, the sodium lignosulfonate of 0.0275kg, the dispersing agent NNO of 0.5kg that add 0.0325kg simultaneously, and above-mentioned additive stirred, add purifying waste water of 6.5kg then, adding density at last is 1.400g/cm
3The sulfuric acid 5kg of (25 ℃), control and cream temperature go out the cream temperature at 30 ℃～45 ℃ less than 65 ℃ in stirring of limit edged and the cream process.
Example 4: the PbO of 50kg73%～85% is added in the paste mixing machine, the fiber, 0.16kg carbon black, the barium sulfate of 0.35kg, the sodium lignosulfonate of 0.035kg, the dispersing agent NNO of 0.6kg that add 0.032kg simultaneously, and above-mentioned additive stirred, add purifying waste water of 6kg then, adding density at last is 1.400g/cm
3The sulfuric acid 4.9kg of (25 ℃), control and cream temperature go out the cream temperature at 30 ℃～45 ℃ less than 65 ℃ in stirring of limit edged and the cream process.
Example 5: the PbO of 50kg73%～85% is added in the paste mixing machine, the fiber, 0.17kg carbon black, the barium sulfate of 0.35kg, the sodium lignosulfonate of 0.035kg, the dispersing agent NNO of 0.75kg that add 0.032kg simultaneously, and above-mentioned additive stirred, add purifying waste water of 6kg then, adding density at last is 1.400g/cm
3The sulfuric acid 4.9kg of (25 ℃), control and cream temperature go out the cream temperature at 30 ℃～45 ℃ less than 65 ℃ in stirring of limit edged and the cream process.
The lead plaster of above-mentioned preparation is coated with 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 adopt the normal process manufacturing through 40 ℃, 98%RH.To just give birth to plate then and put the PE dividing plate respectively and form single lattice utmost point group, be assembled into storage battery, produce test cell after battery changes into by the negative living plate of manufacturing of the present invention.
Claims (4)
1. lead-acid accumulator negative pole lead paste that can improve cryogenic property, it is characterized in that: the solid material of described lead plaster is made up of following weight unit's matter: lead powder 100, fiber 0.055～0.065, carbon black 0.25～0.35, barium sulfate 0.65～0.75, dispersing agent NNO 0.55～1.5, lignosulphonic acid receive 0.05～0.07.
2. the lead-acid accumulator negative pole lead paste that improves cryogenic property according to claim 1 is characterized in that: described dispersing agent NNO content is 0.8～1.2.
3. the lead-acid accumulator negative pole lead paste that improves cryogenic property according to claim 2 is characterized in that: PbO content is 73-84% in the described lead powder.
4. according to claim 1 or the 2 or 3 described preparation methods that improve the lead-acid accumulator negative pole lead paste of cryogenic property, it 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. and cream: the pure water that adds raw material weight 10～13% stirs;
C. drench acid: add the sulfuric acid solution of raw material weight 9～10% while stirring with the spray shape, sulfuric acid solution density is 1.40g/cm
3
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| CNB2005100148156A CN1324734C (en) | 2005-08-22 | 2005-08-22 | Lead-acid accumulator cathode diachylon capable of improving low temperature performance and preparing method |
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| CN1324734C CN1324734C (en) | 2007-07-04 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100394633C (en) * | 2006-05-30 | 2008-06-11 | 风帆股份有限公司 | Lead-acid accumulator negative pole lead paste for electric booster vehicle and preparing method |
| CN101567444B (en) * | 2009-06-08 | 2011-06-22 | 风帆股份有限公司 | Preparation method of vale control lead-acid accumulator green plate without crackles |
| CN103247783A (en) * | 2013-04-10 | 2013-08-14 | 陕西凌云蓄电池有限责任公司 | Adding method of carbon black for lead-acid 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 |
| WO2016026200A1 (en) * | 2014-08-21 | 2016-02-25 | 浙江天能电池江苏新能源有限公司 | Storage battery composite additive |
| CN111342043A (en) * | 2020-02-19 | 2020-06-26 | 浙江埃登达新能源材料有限公司 | Starting battery cathode material and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1104376A (en) * | 1994-09-16 | 1995-06-28 | 陈有孝 | Negative-pole active material for fully-sealed maintenance-less accumulator |
| CN2400910Y (en) * | 1999-10-20 | 2000-10-11 | 吉林市泰维电源有限公司 | Valve control sealed lead-acid accumulator |
| JP4135788B2 (en) * | 2002-05-16 | 2008-08-20 | 株式会社プロスタッフ | Additive for lead acid battery |
-
2005
- 2005-08-22 CN CNB2005100148156A patent/CN1324734C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100394633C (en) * | 2006-05-30 | 2008-06-11 | 风帆股份有限公司 | Lead-acid accumulator negative pole lead paste for electric booster vehicle and preparing method |
| CN101567444B (en) * | 2009-06-08 | 2011-06-22 | 风帆股份有限公司 | Preparation method of vale control lead-acid accumulator green plate without crackles |
| CN103904331A (en) * | 2012-12-31 | 2014-07-02 | 陈荣 | Formula of additive for improving low-temperature charge property of lead-acid storage battery |
| CN103247783A (en) * | 2013-04-10 | 2013-08-14 | 陕西凌云蓄电池有限责任公司 | Adding method of carbon black for lead-acid battery |
| WO2016026200A1 (en) * | 2014-08-21 | 2016-02-25 | 浙江天能电池江苏新能源有限公司 | Storage battery composite additive |
| CN111342043A (en) * | 2020-02-19 | 2020-06-26 | 浙江埃登达新能源材料有限公司 | Starting battery cathode material and preparation method thereof |
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Assignee: INDUSTRIAL BATTERY BRANCH, FENGFAN CO., LTD. Assignor: Fengfan Co., Ltd. Contract fulfillment period: 2007.12.20 to 2017.12.20 contract change Contract record no.: 2008130000065 Denomination of invention: Lead-acid accumulator cathode diachylon capable of improving low temperature performance and preparing method Granted publication date: 20070704 License type: Exclusive license Record date: 20081110 |
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Assignee: INDUSTRIAL BATTERY BRANCH, FENGFAN CO., LTD. Assignor: Fengfan Co., Ltd. Contract fulfillment period: 2007.12.20 to 2017.12.20 contract change Contract record no.: 2008130000065 Denomination of invention: Lead-acid accumulator cathode diachylon capable of improving low temperature performance and preparing method Granted publication date: 20070704 License type: Exclusive license Record date: 20081110 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.12.20 TO 2017.12.20; CHANGE OF CONTRACT Name of requester: FENGFAN CO., LTD. INDUSTRY BATTERY BRANCH CO., LTD Effective date: 20081110 |
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