CN1549364A - Negative pole active material for lead-acid colloid accumulator cell - Google Patents
Negative pole active material for lead-acid colloid accumulator cell Download PDFInfo
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- CN1549364A CN1549364A CNA031242855A CN03124285A CN1549364A CN 1549364 A CN1549364 A CN 1549364A CN A031242855 A CNA031242855 A CN A031242855A CN 03124285 A CN03124285 A CN 03124285A CN 1549364 A CN1549364 A CN 1549364A
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- Prior art keywords
- lead
- barium sulfate
- acetylene black
- modified lignin
- sulfuric acid
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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 negative electrode active material for lead-acid colloid storage battery with long circulating service life, good charging and discharging performance and strong weatherability is a paste-like compound which is made up by mixing the following raw materials: (wt%) sulfuric acid 5-10%, deionized water 7-11%, short fibre 0.05-0.2%, modified lignin 0.02-0.10%, barium sulfate 0.1-1.2%, acetylene black 0.05-0.2%, SnO2 0.05-0.2% and the rest lead powder. The adoption of lead-acid colloid storage battery made up by said invention is applicable to energy storage for utilization of solar energy, etc.
Description
Technical field
The present invention relates to the composition of cathode active materials of lead acid accumulator.
Background technology
The VRLA battery, has used as stand-by power supply in occasions such as post and telecommunications, electric power systems since bringing into use the beginning of the nineties in China always, and its handling characteristics is to be in floating charge state at ordinary times, seldom does recycling of repeated charge.The VRLA battery extends to the cycle applications field more and more in recent years, uses, draws fields such as usefulness and electric vehicle as the solar energy energy storage.Be characterized in that storage battery will be subjected to charge and discharge cycles by continuous ground warp, what have need use in rugged environment, and the VRLA battery has exposed the problem of its cycle life weak point and poor reliability like this, and has limited its range of application.
Colloid storage battery, because its electrolyte is a colloid, but do not flow, do not produce characteristics such as sour layering any direction installation and use so have electrolyte, add advantages such as its superior deep-circulating performance, charge acceptance are strong, the overdischarge restorability is good, serviceability temperature is wide, cryogenic property is good, hot properties is stable, the life-span is long, make the domestic upsurge of studying colloid storage battery that started again in recent years.
Sharp solar energy, wind power generation by accumulators store and release electric energy, are the links that solar energy, wind power generation utilize.The plumbic acid colloid storage battery is applied to the occasion of utilizing of solar energy, wind energy, is that the insider pursues.Yet owing to limit by the environment of solar energy, Wind Power Utilization, condition, storage battery usually can be in the deep discharge operating state, can not get timely charging, or undercharge for a long time, thereby causes active material premature deactivation on the accumulator plate and lost efficacy.The inefficacy of tubular colloidal energy-storage battery mainly is due to the sulfation of active material; Flat colloid battery lost efficacy mainly be that positive material, passivation, grid are corroded, due to the both positive and negative polarity active material sulfation etc., so sulfation is the main cause that this type of colloid battery lost efficacy.
Summary of the invention
The present invention will solve the easy premature deactivation of its active material of plumbic acid colloid storage battery that is used for the repeated charge-discharge cycles use and the problem that makes battery failure, plumbic acid colloid storage battery negative active core-shell material of the present invention is provided for this reason, this negative material is as cathode lead plaster, being coated on grid makes negative plate and is applied to the plumbic acid colloid storage battery, can prevent cell active materials premature deactivation inactivation, thereby prolong battery and recycle the life-span, and can reduce the internal resistance of cell, improve the battery low temperature performance.
For addressing the above problem, plumbic acid colloid storage battery of the present invention provides a kind of paste composition with the technical scheme that negative active core-shell material adopts, and its special character is to be benchmark by sulfuric acid 5-10%, deionized water 7-11%, short fiber 0.05-0.2%, modified lignin 0.02-0.10%, barium sulfate 0.1-1.2%, acetylene black 0.05-0.2%, SnO with its weight
2The lead powder of 0.05-0.2% and surplus mixes to be formed.
Its density of sulfuric acid described in the present invention is preferably 1.40g/cm
3
Described barium sulfate, modified lignin, acetylene black and SnO
2Be coccoid, its preferred particle diameter is 12nm-25nm.
Negative material of the present invention, it is suitable adopting following several composition:
This material of-100kg by: (density is 1.40g/cm to sulfuric acid
3) 6kg, deionized water 7kg, short fiber 0.15kg, modified lignin 0.025kg, barium sulfate 0.25kg, acetylene black 0.1kg, SnO
20.1kg and the lead powder of surplus mixes composition.
This material of-100kg by: (density is 1.40g/cm to sulfuric acid
3) 7kg, deionized water 10kg, short fiber 0.09kg, modified lignin 0.04kg, barium sulfate 0.44kg, acetylene black 0.2kg, SnO
20.2kg and the lead powder of surplus mixes composition.
This material of-100kg by: (density is 1.40g/cm to sulfuric acid
3) 8g, deionized water 10.5kg, short fiber 0.06kg, modified lignin 0.054kg, barium sulfate 0.6kg, acetylene black 0.3kg, SnO
20.3kg and the lead powder of surplus mixes composition.
Modified lignin among the present invention is the mixture of oxylignin and Kraft lignin, mainly is from Borregaard Lignotech company (Norway) import.
Material of the present invention is as cathode lead plaster, is coated on to make negative plate on the grid and be applied to the plumbic acid colloid storage battery.
Material of the present invention also can be coated on grid by this way and make negative plate: 1. with modified lignin, barium sulfate, acetylene black, SnO
2Mix with deionized 25% of described amount, make dispersion suspension liquid, 90% of this suspension liquid measure is mixed with the lead powder of the sulfuric acid of described content, the ionized water of remainder (commercial weight 75%), short fiber and described surplus, is mixed with cathode lead plaster, is coated on grid; 2. in coating procedure, again the dispersion suspension liquid of remainder (commercial weight 10%) spray is made negative plate thereon; Or: after 1. being coated on grid by above-mentioned steps, will be coated with in the dispersion suspension liquid that the negative plate of making is soaked in remaining part about 2 minutes again, and make suspension absorption and infiltrate in the lead plaster layer.
Negative material of the present invention also claims negative active core-shell material.
Barium sulfate among the present invention is as inorganic additive, can become the crystal seed of lead sulfate crystal effectively, the lead sulfate crystal refinement with electrical insulating property that battery is generated on the negative plate in charge and discharge process prevents that the lead sulfate crystal from growing up deposition and the conductivity that reduces pole plate is obstructed battery charging and discharging.
Modified lignin among the present invention is as organic expander, and it can be adsorbed in the lead sulfate plane of crystal consumingly, slows down or stop the growth of lead sulfate crystal, plays the effect of crystal growth inhibitor, suppresses or slows down negative pole sulfation phenomenon.With respect to common lignosulphonates, the existence of described modified lignin, also to battery reduce self discharge, to improve heavy-current discharge performance helpful.
Acetylene black and SnO
2As the electric conducting material additive, its adding can improve the conductivity of negative plate lead plaster layer, improves contacting between lead plaster layer and grid simultaneously, improves the conductivity of the two; This additive also is scattered in the lead plaster laminar surface more, has overcome polar board surface because of generating the conduction bad phenomenon that lead sulfate causes.
Be used for the storage battery that solar energy utilizes occasion, require widely to the ambient temperature scope of application, low temperature performance is good, and hot properties is stable.General swelling agent is subject to the oxidation of battery precipitated oxygen, and is at high temperature more obvious, causes the swelling agent passivation, causes that negative electrode active material dwindles, and specific area descends, thereby causes the battery capacity loss.Add the modified lignin and the barium sulfate of appropriate amount among the present invention, it at high temperature is difficult for passivation, can improve the cycle performance of negative pole simultaneously, improves output current, and role is obvious at low temperatures, is more suitable in part state-of-charge (PSOC) field battery.
Adopt the present invention, can improve the conductivity of this negative electrode active material on the negative plate, thereby improve the charge acceptance of electrode, and raising output current, improve the high-rate battery discharge performance, prolong the life-span that recycles of battery simultaneously, increase battery applications ambient temperature range of living in, make battery be suitable for using under the more abominable occasion of environment.These beneficial effects are because of specific composition of the present invention.
Apply the 2V200Ah plumbic acid colloid storage battery that negative plate that grid makes is made with negative material of the present invention, 20% discharge, cycle life is 3200 times, 40% discharge cycles life-span was 1300 times, 60%DOD discharge follows not that the life-span is 900 times, and the 100%DOD discharge cycles life-span reaches more than 500 times.Wherein under-10 ℃ of situations, the 20hr discharge is equivalent to more than 80% of capacity under the normal temperature, shows superior low temperature performance, adopts and owes charging procedure, and colloid battery is investigated, and does not find the phenomenon of polar plate sulfation.
Embodiment
The component of the embodiment of the invention 1～7 and content thereof are provided by following table 1, and numeral is the kg number in the table, and all components total amount is 100kg.
| Component | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 |
| Barium sulfate | ??0.2 | ??0.4 | ??0.7 | ??0.5 | ??1.0 | ??1.2 | ??0.6 |
| Modified lignin | ??0.02 | ??0.03 | ??0.06 | ??0.07 | ??0.04 | ??0.1 | ??0.05 |
| Acetylene black | ??0.05 | ??0.1 | ??0.15 | ??0.05 | ??0.08 | ??0.12 | ??0.2 |
| ??SnO 2 | ??0.05 | ??0.2 | ??0.05 | ??0.15 | ??0.12 | ??0.18 | ??0.1 |
| Short fiber | ??0.06 | ??0.16 | ??0.05 | ??0.10 | ??0.12 | ??0.08 | ??0.05 |
| Sulfuric acid | ??9.5 | ??6.00 | ??9.0 | ??8.0 | ??7.5 | ??9.0 | ??10.00 |
| Deionized water | ??7.50 | ??9.50 | ??8.0 | ??8.0 | ??8.50 | ??9.50 | ??10.50 |
| Lead powder | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
Claims (6)
1, plumbic acid colloid storage battery negative active core-shell material, be a kind of paste composition, it is characterized in that with its weight be benchmark by sulfuric acid 5-10%, deionized water 7-11%, short fiber 0.05-0.2%, modified lignin 0.02-0.10%, barium sulfate 0.1-1.2%, acetylene black 0.05-0.2%, SnO
2The lead powder of 0.05-0.2% and surplus mixes to be formed.
2, negative material as claimed in claim 1 is characterized in that its density of described sulfuric acid is 1.40g/cm
3
3, negative material as claimed in claim 2 is characterized in that barium sulfate, modified lignin, acetylene black and SnO
2For its grain diameter of coccoid is 12nm-25nm.
4, negative material as claimed in claim 3, it is characterized in that this material of 100kg by: (density is 1.40g/cm to sulfuric acid
3) 6kg, deionized water 7kg, short fiber 0.15kg, modified lignin 0.025kg, barium sulfate 0.25kg, acetylene black 0.1kg, SnO
20.1kg and the lead powder of surplus mixes composition.
5, negative material as claimed in claim 3, it is characterized in that this material of 100kg by: (density is 1.40g/cm to sulfuric acid
3) 7kg, deionized water 10kg, short fiber 0.09kg, modified lignin 0.04kg, barium sulfate 0.44kg, acetylene black 0.2kg, SnO
20.2kg form to become with the lead powder mixing of surplus.
6, negative material as claimed in claim 3, it is characterized in that this material of 100kg by: (density is 1.40g/cm to sulfuric acid
3) 8kg, deionized water 10.5kg, short fiber 0.06kg, modified lignin 0.054kg, barium sulfate 0.6kg, acetylene black 0.3kg, SnO
20.3kg and the lead powder of surplus mixes composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031242855A CN1260839C (en) | 2003-05-07 | 2003-05-07 | Negative pole active material for lead-acid colloid accumulator cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031242855A CN1260839C (en) | 2003-05-07 | 2003-05-07 | Negative pole active material for lead-acid colloid accumulator cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1549364A true CN1549364A (en) | 2004-11-24 |
| CN1260839C CN1260839C (en) | 2006-06-21 |
Family
ID=34321631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031242855A Expired - Fee Related CN1260839C (en) | 2003-05-07 | 2003-05-07 | Negative pole active material for lead-acid colloid accumulator cell |
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| CN (1) | CN1260839C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341175C (en) * | 2005-10-14 | 2007-10-03 | 周明明 | Lead-acid battery colloid polar plate and manufacturing technology thereof |
| RU2454756C1 (en) * | 2011-03-05 | 2012-06-27 | Общество с ограниченной ответственностью "Новгородская Аккумуляторная Компания" | Paste for negative electrode of lead-acid battery and method of its preparation |
| 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 |
| CN113224394A (en) * | 2021-04-20 | 2021-08-06 | 淄博火炬能源有限责任公司 | Low-temperature lead-carbon battery electrolyte |
-
2003
- 2003-05-07 CN CNB031242855A patent/CN1260839C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341175C (en) * | 2005-10-14 | 2007-10-03 | 周明明 | Lead-acid battery colloid polar plate and manufacturing technology thereof |
| RU2454756C1 (en) * | 2011-03-05 | 2012-06-27 | Общество с ограниченной ответственностью "Новгородская Аккумуляторная Компания" | Paste for negative electrode of lead-acid battery and method of its preparation |
| WO2012121627A1 (en) * | 2011-03-05 | 2012-09-13 | Общеcтво С Ограниченной Отвественностью "Новогородская Аккумуляторная Компания" | Paste for the negative electrode of a lead-acid battery and method for manufacturing said paste |
| 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 |
| CN113224394A (en) * | 2021-04-20 | 2021-08-06 | 淄博火炬能源有限责任公司 | Low-temperature lead-carbon battery electrolyte |
| CN113224394B (en) * | 2021-04-20 | 2022-05-03 | 淄博火炬能源有限责任公司 | Low-temperature lead-carbon battery electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1260839C (en) | 2006-06-21 |
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