CN1222070C - Colloid electrolyte for accumulator - Google Patents
Colloid electrolyte for accumulator Download PDFInfo
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- CN1222070C CN1222070C CNB021523517A CN02152351A CN1222070C CN 1222070 C CN1222070 C CN 1222070C CN B021523517 A CNB021523517 A CN B021523517A CN 02152351 A CN02152351 A CN 02152351A CN 1222070 C CN1222070 C CN 1222070C
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- electrolyte
- accumulator
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- silicon dioxide
- battery
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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 present invention relates to an accumulator colloid electrolyte which is convenient to fill and has the functions of prolonging the service life of batteries and enhancing the heavy-current discharging performance of batteries. The colloid electrolyte is composed of 2 to 12 wt% of nanometer silicon dioxide, 0.01 to 0.2 wt% of polyacrylamide, 0.1 to 1.0 wt% of phosphoric acid and the balance of sulphuric acid water solution whose concentration in percentage by weight is from 35% to 40%. The present invention is suitable for being used as an accumulator colloid electrolyte.
Description
Technical field
The present invention relates to the electrolyte of storage battery.
Background technology
At present the domestic production valve-regulated lead-acid battery has two class technology, first glass fibre separator technology, and it two is colloid (Gel) technology.Because there are defectives such as short and poor reliability in relative useful life in the valve-regulated lead-acid battery that the glass fibre separator technology is produced, thus in recent years much the expert turn to the colloid Study on Technology one after another.Because colloidal electrolyte has nonflowing character, not leakiness acid, can prevent that active material from coming off, reducing advantages such as self discharge, extending battery life, has remarkable advantages in application process.Yet with regard to colloid battery, the technology of most critical is a colloidal electrolyte formula, and different prescriptions is very big to the performance impact of colloidal electrolyte.At present, the colloidal electrolyte of domestic production is primary raw material preparation with sulfuric acid and Ludox mainly, discloses as the Chinese invention patent ublic specification of application of notification number CN1061113A, CN1169040A, CN1163492A.There is poor, the easy aquation, aging fast, easily dry and produce phenomenon such as be full of cracks of thixotropy mostly in the colloid made from Ludox, causes accumulator internal resistance to increase, and heavy-current discharge performance descends, and self discharge is quick, and battery capacity decline recycles the lost of life.
Summary of the invention
The present invention will solve known Colliod electrolyte for accumulator because of above-mentioned defective causes the problem that high-rate battery discharge poor performance, self discharge are quick, useful life is short, and Colliod electrolyte for accumulator of the present invention is provided for this reason.
For addressing the above problem, its special character of Colliod electrolyte for accumulator of the present invention is in this colloidal electrolyte weight, component by following percetage by weight is formed: nanometer grade silica 2%～12%, polyacrylamide 0.01%～0.2%, phosphoric acid 0.1%～1.0%, surplus are aqueous sulfuric acid.
The component of described percetage by weight is preferably: nanometer grade silica 4%～8%, and polyacrylamide 0.1%～0.2%, phosphoric acid 0.1%～1.0%, surplus is an aqueous sulfuric acid.
Described aqueous sulfuric acid preferred weight percentage concentration is 35%～40%.
Used nanometer grade silica (the SiO of the present invention
2), produced by " vapor phase method ", often be referred to as " aerosil " in the industry, powdered.
The used aerosil of the present invention, its particle size is very important, particle diameter is during less than 5nm, the gelation rate of colloid is very fast, form the gel densification, hard, intensity is big, it is poor to cut rare back thixotropic property, is unfavorable for can; And when particle diameter during greater than 50nm, surface activity reduces, and gel time is very long, and good although gel is cut rare property, it is very slow that three-dimensional network forms, and be difficult to obtain the high-quality gelinite, and the colloid hydration phenomena is serious.Be softness and the intensity of taking into account gel, its particle diameter of the silicon dioxide that is adopted answers thickness suitable, and colloid could form stable three-dimensional network, and gels-soft is and flexible, and thixotropy is better.Its particle diameter of the used silicon dioxide of the present invention is preferably 10nm～50nm, and wherein particle diameter is 50% (weight) that accounts for of 20nm～30nm.
Nanometer grade silica is the gelatinous mass of this colloidal electrolyte, also can be referred to as gel.Dioxide-containing silica changes in certain limit (described 2%～12%), bigger to colloidal electrolyte thixotropy, viscosity, gel strength, stability and conductivity influence, dioxide-containing silica of the present invention is that 4%～8% colloidal electrolyte of making has better comprehensive performance.
Add surfactant and can change the surface state of gel silicon dioxide granule, play and stop the gel particle accumulation, the effect of delay gelatinizing process, stable colloid condition therefrom is so the surfactant among the present invention can be considered deflocculant.Surfactant is a high molecular polymer, existing simultaneously in its molecule has the A structure of strong affinity and dispersant is had the B structure of fine compatibility adsorbent, when being added to them in the sol system, structure A is adsorbed on the surface of colloidal particle (silicon dioxide) securely, structure B then is stretched in the decentralized medium, just formed a stable adsorption layer like this on the colloidal particle surface, when particle is close, because macromolecular existence, formed steric hindrance barrier, made to be difficult between particle react, therefore the existence of the surfactant of this stabilization has been arranged, colloidal gel speed slows down, gelling performance is improved, and makes colloid be in the stable performance state all the time, thus, both improve the performance of battery, be convenient to the can of colloid again.The consumption of surfactant has requirement.Surfactant of the present invention can adopt polyacrylamide, and its addition is 0.01%～0.2% of a colloid total weight, and preferred 0.1%～0.2%.
Phosphoric acid adds phosphoric acid and can effectively reduce the electrolyte internal resistance as a kind of additive, helps ions diffusion, improves the contact performance of colloidal electrolyte and pole plate, and reduces self-discharge of battery effectively, can make battery capacity improve about 10%.
The used nanometer grade silica of the present invention is the external product of import, and polyacrylamide, phosphoric acid and sulfuric acid are got homemade getting final product.
Described component is placed container by silicon dioxide, surfactant, phosphoric acid and sulfuric acid solution charging sequence, stir, mix, promptly get colloidal electrolyte of the present invention.
Colloidal electrolyte of the present invention, owing to form by nanometer grade silica, surfactant, additive (phosphoric acid) and the sulfuric acid solution that plays the electrolysis effect, each component amount of getting is appropriate, so colloid thixotropy and having good stability, and can directly pour into and be used for storage battery production, (general filling process adopts before the perfusion colloidal electrolyte needn't to carry out loaded down with trivial details filling process, inject used dilute sulfuric acid earlier, soaked 30 minutes, after dilute sulfuric acid soaks into pole plate and dividing plate, go unnecessary acid solution in the battery, inject the colloidal electrolyte that contains different additive respectively).With the storage battery that colloidal electrolyte of the present invention is made, long service life.Colloidal electrolyte of the present invention can slow down coming off of plate active material in the battery cyclic process, the active material that comes off with retardance free, reduce the possibility of battery micro-short circuit, avoid occurring the electrolyte stratification phenomenon, overcome pole plate bundle homogeneous corrosion, slow down the battery capacity decay, so greatly prolonged the life-span of battery.Next is to have good low-temperature high-current discharge performance, and the active material reaction speed reduces during low temperature generally speaking, and the diffusive migration speed of ion slows down, and produces the negative pole passivation, thereby influences the low-temperature high-current discharge performance.The battery low temperature performance made from the colloidal electrolyte perfusion of invention is good, and this is because the suction-operated of silicon gel has reduced near the PbSO of electrode
4Degree of supersaturation, the PbSO that negative terminal surface is formed
4Crystal grain is thick relatively, has prolonged the covering on anticathode surface relatively, thereby has improved the low temperature performance of negative plate.Colloidal electrolyte of the present invention can effectively suppress the brown lead oxide spontaneous reduction, slows down storage battery self discharge reaction speed, and the self discharge of battery is obviously slowed down, and battery was placed 1 year, and the actual capacity that keeps is 85% of a rated capacity still, and the internal resistance of cell is little.On probation showing, the 12V10AH electrokinetic cell that utilizes colloidal electrolyte of the present invention to make, 100%DOD cycle life reaches 600 times, be 3 times of common AGM battery cycle life, other performance meets the requirement of mechanical industry standard JB/T10262, as the supporting power supply of electric bicycle, reach more than 2 years its actual life.
Embodiment
Example 1 Colliod electrolyte for accumulator, per 100 these colloidal electrolytes of gram are evenly mixed by aqueous sulfuric acid 92.85 grams of nanometer grade silica 6.5 grams, polyacrylamide 0.15 gram, phosphoric acid 0.5 gram and concentration 36% (W/W).
Example 2 Colliod electrolyte for accumulator, per 100 these colloidal electrolytes of gram are evenly mixed by aqueous sulfuric acid 89.8 grams of nanometer grade silica 9.0 grams, polyacrylamide 0.2 gram, phosphatase 11 .0 gram and concentration 38% (W/W).
Example 3 Colliod electrolyte for accumulator, per 100 these colloidal electrolytes of gram are evenly mixed by aqueous sulfuric acid 96.77 grams of nanometer grade silica 3.0 grams, polyacrylamide 0.08 gram, phosphoric acid 0.15 gram and concentration 40% (W/W).
Example 4 Colliod electrolyte for accumulator, per 100 these colloidal electrolytes of gram are evenly mixed by aqueous sulfuric acid 88.47 grams of nanometer grade silica 11.0 grams, polyacrylamide 0.03 gram, phosphoric acid 0.5 gram and concentration 36% (W/W).
Claims (5)
1, Colliod electrolyte for accumulator, it is characterized in that this colloidal electrolyte weight meter, form: the silicon dioxide 2%～12% of particle diameter 5nm～50nm, polyacrylamide 0.01%～0.2% by the component of following percetage by weight, phosphoric acid 0.1%～1.0%, surplus are aqueous sulfuric acid.
2, Colliod electrolyte for accumulator as claimed in claim 1, the component that it is characterized in that described percetage by weight is: the silicon dioxide 4%～8% of particle diameter 5nm～50nm, polyacrylamide 0.01%～0.2%, phosphoric acid 0.1%～1.0%, surplus is an aqueous sulfuric acid.
3, Colliod electrolyte for accumulator as claimed in claim 1 or 2, the concentration expressed in percentage by weight that it is characterized in that described aqueous sulfuric acid is 35%～40%.
4, Colliod electrolyte for accumulator as claimed in claim 3, the particle diameter that it is characterized in that described silicon dioxide is 10nm～50nm.
5, Colliod electrolyte for accumulator as claimed in claim 4 is characterized in that described silicon dioxide, wherein particle diameter be 20nm～30nm account for 50% of silicon dioxide total weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021523517A CN1222070C (en) | 2002-11-27 | 2002-11-27 | Colloid electrolyte for accumulator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021523517A CN1222070C (en) | 2002-11-27 | 2002-11-27 | Colloid electrolyte for accumulator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1503393A CN1503393A (en) | 2004-06-09 |
| CN1222070C true CN1222070C (en) | 2005-10-05 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021523517A Expired - Lifetime CN1222070C (en) | 2002-11-27 | 2002-11-27 | Colloid electrolyte for accumulator |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100483833C (en) * | 2004-10-25 | 2009-04-29 | 深圳理士奥电源技术有限公司 | Nanometer-level high composite electrolyte and its preparing method |
| CN101246968B (en) * | 2007-07-30 | 2010-06-09 | 华南师范大学 | Nano-gas-phase SiO2 colloid electrolytic solution and its preparing method and colloid accumulator |
| CN101834316A (en) * | 2010-05-24 | 2010-09-15 | 伊奎桦 | Colloidal electrolyte for storage battery |
| CN102013521B (en) * | 2010-10-27 | 2013-08-07 | 华南师范大学 | Silicon mixed colloid electrolyte for lead acid storage batteries |
| CN102201599A (en) * | 2011-04-03 | 2011-09-28 | 拾景阁 | Thixotropic nano-colloid electrolyte used for lead-acid battery of mining locomotive |
| CN102324575A (en) * | 2011-09-28 | 2012-01-18 | 江苏富思特电源有限公司 | Gel battery electrolyte and manufacturing method |
| CN102593530A (en) * | 2012-02-27 | 2012-07-18 | 超威电源有限公司 | Colloidal electrolyte for power battery |
| TW201424084A (en) * | 2012-12-14 | 2014-06-16 | Taiwan Yuasa Battery Co Ltd | Electrolyte additive for lead acid battery |
| CN105280962B (en) * | 2015-09-17 | 2017-12-08 | 高文梅 | High-performance electrolyte solution and preparation method thereof |
| CN108493496A (en) * | 2018-04-09 | 2018-09-04 | 海志电源技术（赣州）有限公司 | A kind of high-performance nano colloid power battery and preparation method |
| CN109860480A (en) * | 2018-12-29 | 2019-06-07 | 桑顿新能源科技有限公司 | A kind of gel state lithium ion battery diaphragm and preparation method thereof |
-
2002
- 2002-11-27 CN CNB021523517A patent/CN1222070C/en not_active Expired - Lifetime
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| CN1503393A (en) | 2004-06-09 |
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