CN1767248A - Nanometer-level high composite electrolyte and its preparing method - Google Patents
Nanometer-level high composite electrolyte and its preparing method Download PDFInfo
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- CN1767248A CN1767248A CNA200410040933XA CN200410040933A CN1767248A CN 1767248 A CN1767248 A CN 1767248A CN A200410040933X A CNA200410040933X A CN A200410040933XA CN 200410040933 A CN200410040933 A CN 200410040933A CN 1767248 A CN1767248 A CN 1767248A
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- nanoscale
- composite electrolyte
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- pure water
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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
Abstract
The invention relates to a nanometer high compound electrolytic solution which comprises: dilute sulphuric acid, pure water and nanometer high scattering SiO2 (by weight rate): dilute sulphuric acid:pure water:nanometer high scattering SiO2=1:2:16. The grain size of the nanometer high scattering SiO2 particle is 50-500nm. The preparing method comprises the following steps: 1) mixing the nanometer high scattering SiO2 and the pure water by weight rate, cooling it, wherein the temperature of the mixing course is 60-80 DEG C; 2) adding the dilute sulphuric acid into the cooled solution and stirring with high speed until stirring evenly.
Description
[technical field]
The present invention relates to a kind of electrolyte that is used for sealed lead acid battery.
[background technology]
The sealed lead acid storage battery in fields such as electrolyte is widely used in circulating, standby, traction, power or starting.The electrolyte of these sealed lead acid batteries generally comprises dilute sulfuric acid and silicate, and it solidifies by stirring, leave standstill, treating, promptly get the electrolyte of colloidal after the emulsification, slaking certain hour.Yet, this kind electrolyte is deposited in use and have aquation (water is separated out) and the bigger problem of crackle in the process from colloid, and because silicate granules is bigger, so bad dispersibility, there is certain sensitiveness in temperature, thermal capacitance causes for a short time that dehydration is still big, conduction is inhomogeneous, heavy-current discharge performance circulation ability weak, storage battery is relatively poor, and causes sealed lead accumulator to produce the problem of thermal runaway easily.
[summary of the invention]
The object of the present invention is to provide high composite electrolyte of nanoscale that a kind of heavy-current discharge performance is good, charge acceptance is high, circulating effect is good and preparation method thereof.
The object of the present invention is achieved like this: the high composite electrolyte of this nanoscale comprises dilute sulfuric acid, pure water and siliceous nanometer materials.
Described siliceous nanometer materials are nanoscale polymolecularity SiO
2
The dispersed SiO of described nanoscale
2Particle grain size is 50～500nm.
Described nanoscale polymolecularity SiO
2, pure water and dilute sulfuric acid weight ratio be selected from following ratio: 3: 5: (40～42), 3: (6～7): (43～48), 1: 2: 16.
Also comprise additive, the weight ratio of this additive and pure water is (0.7 ± 0.02): 100.
The preparation method of the high composite electrolyte of a kind of nanoscale comprises the steps:
1) by weight with nanoscale polymolecularity SiO
2Mix with pure water, cooled off after mixing, wherein the temperature of solution is 60～80 ℃ in the mixed process;
2) in cooled solution, add dilute sulfuric acid and high-speed stirred until stirring.
The speed of described high-speed stirred is 1200～1500 rev/mins.
In the described high-speed stirred process, the temperature of mixed liquor is 30 ℃ during stirring.
Compared with prior art, the present invention has following advantage: 1) because electrolyte has used siliceous nanometer materials, this nano material has the big advantage of thermal capacitance, and has a heat conductive performance of metalloid, after nano-substance mixes, add that the colloid water content is higher than the AGM type, so thermal capacitance increases substantially, heat conduction just more all even equilibriums have reduced the danger that thermal runaway causes battery malfunction; 2) under cryogenic conditions (as-5 ℃), it is little that the colloid of the high composite electrolyte of use nanometer is influenced by viscosity, so heavy-current discharge performance is good; 3) because the high composite electrolyte of nanoscale is a colloid, and colloid has a large amount of moisture, on the dehydration from the use of sealed cell caused aspect the life of storage battery termination, its life-span than the valve-control sealed storage battery of AGM approximately prolonged 30%; 4) owing to contain additive, so improved the stability and the uniformity of colloidal electrolyte, prevent aquation (water is separated out) and produce continuous crack, and only can produce trickle intersection crackle that the gas maximum that reaches sealed cell is compound from glue.
[embodiment]
The high composite electrolyte of nanoscale of the present invention is a colloid, and its composition comprises siliceous nanometer materials, dilute sulfuric acid, additive and pure water.In the present embodiment, these siliceous nanometer materials are nanoscale polymolecularity SiO
2, its particle grain size is about 50～500nm, and it can adopt the nanoscale SiO of prior art
2, this nanoscale SiO
2Particle is to make by existing diffusion method.The concentration range of dilute sulfuric acid is 1.370～1.420g/cm
3, in this concentration range, make other composition of electrolyte that dispersiveness is preferably arranged, thereby be convenient to the preparation of electrolyte.Additive mainly is stability and the uniformity that is used to improve colloid, prevent aquation (water is separated out) and produce continuous crack from glue, only produce trickle intersection crackle, the gas maximum that reaches sealed cell is compound, and the additive that is adopted is mainly polymerization amide-type, polymerization alcohols.Nanoscale polymolecularity SiO
2, the weight ratio between pure water and the dilute sulfuric acid is 1: 2: 16, the weight ratio of pure water and additive is 100: (0.7 ± 0.02).
A kind of concrete preparation method of the high composite electrolyte of this nanoscale comprises the steps: 1) the additive input of getting pure water 100g and trace mixes in the container of usefulness (as mixing kettle), and both are mixed, and forms pure water solution; 2) with 50g nanoscale polymolecularity SiO
2Gradation adds in the pure water solution configure, and the temperature in the mixing kettle is risen to 60～80 ℃ and keep this temperature, adopts the high-speed mixing method continuous stirring to mix until solution, cooling rapidly then, and this moment, solution was colloidal; Add the dilution heat of sulfuric acid 800g for preparing when 3) being cooled to 5 ℃ and utilize high-speed mixing method to stir fast, stirring, then electrolyte can be standby.
In the step 1), additive mainly is stability and the uniformity that is used to improve colloid, prevents aquation (water is separated out) and produce continuous crack from glue, and only produce trickle intersection crackle, the gas maximum that reaches sealed cell is compound, also can add additive certainly.
Step 2) in, the temperature in the mixing kettle remains on 60～80 ℃, so the temperature of solution is 60～80 ℃ in the whipping process; High-speed mixing method is meant in preparation and adopted during colloid mixing speed to surpass 500 rev/mins alr mode, and general mixing speed is 500～1500 rev/mins, and the purpose of this high-speed stirred is nanoscale polymolecularity SiO
2Be uniformly dispersed with additive, make it easy to reach balanced to greatest extent, thereby guarantee the uniform stability and the uniformity of colloidal materials with the dilute sulfuric acid of water and adding thereafter.
In the step 3), the temperature of the dilute sulfuric acid of adding is 20～50 ℃, because in this scope, dilute sulfuric acid has the good mobility energy after adding colloid, can guarantee the equilibrium and the consistency of disperseing to greatest extent, and then can guarantee the stability of colloid and harmonious.In step 2) in mixed liquor add dilution heat of sulfuric acid when being cooled to 5 ℃, be because the mixing of dilution heat of sulfuric acid and pure water solution is exothermic reaction, in order to control and to simplify variable factor in the reaction, improve the thermal capacitance of dilution heat of sulfuric acid, make that the temperature of mixed liquor is unlikely super design temperature in the course of reaction, can guarantee that also mixed liquor has lower viscosity and good mobility energy simultaneously.
In the above-mentioned preparation process, control evenly and variations in temperature little, if manufacture process is inhomogeneous, then the nano-grade matter dispersion is inhomogeneous, thereby causes the colloidal electrolyte different in kind, thereby influences the performance of storage battery, and make variations in temperature big, then production process is restive, and can the quick thixotroping of generation part solidify in manufacture process, causes colloid inhomogeneous and thinning.
Manufacturing environment requires temperature constant, solidifies thereby can prevent to produce in the production process the quick thixotroping of part, and then causes colloid inhomogeneous and thinning, so the general environment temperature is controlled at 25 ± 10 ℃, this ambient temperature range also is convenient to operation.
The high composite electrolyte of nanoscale of the present invention can adopt different proportioning components according to the different temperature conditions in each department, as in the torrid zone when (average temperature of the whole year is higher than 23 ℃), and nanoscale polymolecularity SiO
2, pure water and dilute sulfuric acid weight ratio be: 3: 5: (40～42); As in the frigid zone when (average temperature of the whole year is lower than 15 ℃), nanoscale polymolecularity SiO
2, pure water and dilute sulfuric acid weight ratio be: 3: (6～7): (43～48); In the temperate zone when (average temperature of the whole year is 15～23 ℃), nanoscale polymolecularity SiO then
2, pure water and dilute sulfuric acid weight ratio be: 1: 2: 16.This nanoscale polymolecularity SiO
2Can also substitute with other siliceous nanometer materials, receive as the nanoscale metasilicic acid.
The operation principle of the high composite electrolyte of nanoscale of the present invention is as follows: owing to adopt nano material, institute is so that colloidal solid drops to nanoscale, granule surface area is increased, activity significantly improves, reduced the nucleus effect between the particle simultaneously, made the colloid uniformity more stable, the electrolyte denseness is along with increase, thixotropic property increases, and the thermal capacitance ability significantly strengthens; When charge in batteries, sulfuric acid concentration increases in the electrolyte, makes it " thickening " and produces with trickle electrolyte slight crack, and the oxygen that makes sealing lead acid accumulator recombination reaction efficient again obtains performance; During battery discharging, sulfuric acid is consumed in the electrolyte, and it is thinning that concentration reduces electrolyte, becomes the preceding gluey form of perfusion battery (but mobile remarkable decline) again, so moves in circles.
Form one is the battery of use composite electrolyte of the present invention and the overcharge test of AGM battery, this overcharge test adopts greater than valve-control sealed battery limitation charging current 0.3C AGM, the sample battery 12V38AH trickle charge of same specification 72 hours, observes and the variations in temperature of record housing distortion time and outer surface.
Form one
| Sequence number | Project | Measuring Time (h) (with) | Table to temperature rise (℃) (with initial ratio) | Deformation time (h) |
| 1 | AGM12V38 AH battery | 2h | 15.5 | Housing begins distortion during 2.2h, and 3.1h is gross distortion |
| 5h | 36.3 |
| 10h | 41.2 | |||
| 2 | Sample 12V 38AH battery | 2h | 11.4 | Housing is not seen distortion during 3h, and housing begins distortion during 7.2h, and 9h has begun gross distortion |
| 5h | 28 | |||
| 10h | 35.5 | |||
| 15h | 37 | |||
| 3 | AGM12V38 AH battery | 3h | 18.2 | Housing obviously is out of shape during 3h, and 3.1h is gross distortion |
| 6h | 35.9 | |||
| 10h | 41.5 | |||
| 4 | Sample 12V 38AH battery | 3h | 12.8 | Housing is not seen distortion during 3h, and housing begins distortion during 7.2h, and 9h has begun gross distortion |
| 6h | 29.1 | |||
| 10h | 35.2 | |||
| 15h | 37.2 |
By above table as can be seen, under the situation with the same current charging, the temperature lift-off value of the battery of the high composite electrolyte of use nanoscale is more much smaller than common batteries, and this proof uses thermal capacitance of the battery of the high composite electrolyte of nanoscale also to increase a lot.Simultaneously,,, show that promptly most of electric power accepted by battery, therefore the charge acceptance height is described so infer the little energy be used to generate heat because the temperature rise of charging is little.
Because electrolyte has used nano level material, this nano-substance has the big advantage of thermal capacitance, and has a heat conductive performance of metalloid, after nano-substance mixes, add that the colloid water content is higher than the AGM type, so thermal capacitance increases substantially just more all even equilibriums of heat conduction, and then enlarged the scope of application of storage battery, reduced the danger that thermal runaway causes using the battery malfunction of this electrolyte.Under cryogenic conditions (as-5 ℃), it is little that the colloid of the high composite electrolyte of use nanometer is influenced by viscosity, so heavy-current discharge performance is good.In addition, because the high composite electrolyte of nanoscale is colloid, colloid has a large amount of moisture, and on the dehydration from the use of sealed cell caused aspect the life of storage battery termination, its life-span than the valve-control sealed storage battery of AGM approximately prolonged 30%.
Claims (10)
1. the high composite electrolyte of nanoscale comprises dilute sulfuric acid and pure water, it is characterized in that: also comprise siliceous nanometer materials.
2. the high composite electrolyte of nanoscale as claimed in claim 1 is characterized in that: described siliceous nanometer materials are nanoscale polymolecularity SiO
2
3. the high composite electrolyte of nanoscale as claimed in claim 2 is characterized in that: described nanoscale polymolecularity SiO
2Particle grain size is 50～500nm.
4. the high composite electrolyte of nanoscale as claimed in claim 3 is characterized in that: described nanoscale polymolecularity SiO
2, pure water and dilute sulfuric acid weight ratio be selected from following ratio: 3: 5: (40～42), 3: (6～7): (43～48), 1: 2: 16.
5. as any high composite electrolyte of described nanoscale among the claim 1-4, it is characterized in that: also comprise additive, the weight ratio of this additive and pure water is (0.7 ± 0.02): 100.
6. as any high composite electrolyte of described nanoscale among the claim 1-4, it is characterized in that: the concentration of described dilute sulfuric acid is 1.370～1.420g/cm
3
7. the preparation method of the high composite electrolyte of nanoscale as claimed in claim 1 is characterized in that: comprise the steps:
1) by weight with nanoscale polymolecularity SiO
2Mix with pure water, cooled off after mixing,
Wherein the temperature of solution is 60～80 ℃ in the mixed process;
2) in cooled solution, add dilute sulfuric acid and high-speed stirred until stirring.
8. the high composite electrolyte of nanoscale as claimed in claim 7 is characterized in that: the speed of described high-speed stirred is 500～1500 rev/mins.
9. as claim 7 or the high composite electrolyte of 8 described nanoscales, it is characterized in that: the concentration of described dilute sulfuric acid is 1.370～1.420g/cm
3, the temperature of this dilute sulfuric acid is 20～50 ℃.
10. as claim 7 or the high composite electrolyte of 8 described nanoscales, it is characterized in that: described step 2), the temperature of mixed liquor is 30 ℃ during stirring.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410040933XA CN100483833C (en) | 2004-10-25 | 2004-10-25 | Nanometer-level high composite electrolyte and its preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410040933XA CN100483833C (en) | 2004-10-25 | 2004-10-25 | Nanometer-level high composite electrolyte and its preparing method |
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|---|---|
| CN1767248A true CN1767248A (en) | 2006-05-03 |
| CN100483833C CN100483833C (en) | 2009-04-29 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103456999A (en) * | 2013-09-13 | 2013-12-18 | 仇金生 | Electrolyte solution for manufacturing microcrystal storage battery and preparation method of electrolyte solution |
| CN103682330A (en) * | 2013-11-15 | 2014-03-26 | 超威电源有限公司 | Internal formation lead plaster preparation process |
| CN103682497A (en) * | 2013-11-15 | 2014-03-26 | 超威电源有限公司 | Mixing process of container formation battery |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1222070C (en) * | 2002-11-27 | 2005-10-05 | 浙江南都电源动力股份有限公司 | Colloid electrolyte for accumulator |
| CN1219336C (en) * | 2002-12-04 | 2005-09-14 | 中国科学院金属研究所 | Addition agent for lead-acid storage battery and method for making same |
| CN1324754C (en) * | 2003-04-07 | 2007-07-04 | 威海文隆电源集团有限公司 | Lead-acid cell colloid electrolyte |
-
2004
- 2004-10-25 CN CNB200410040933XA patent/CN100483833C/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103456999A (en) * | 2013-09-13 | 2013-12-18 | 仇金生 | Electrolyte solution for manufacturing microcrystal storage battery and preparation method of electrolyte solution |
| CN103682330A (en) * | 2013-11-15 | 2014-03-26 | 超威电源有限公司 | Internal formation lead plaster preparation process |
| CN103682497A (en) * | 2013-11-15 | 2014-03-26 | 超威电源有限公司 | Mixing process of container formation battery |
| CN103682497B (en) * | 2013-11-15 | 2016-04-06 | 超威电源有限公司 | One is internalized into battery and closes cream technique |
| CN103682330B (en) * | 2013-11-15 | 2016-04-06 | 超威电源有限公司 | One is internalized into lead plaster and closes technique processed |
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| CN100483833C (en) | 2009-04-29 |
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Application publication date: 20060503 Assignee: JIANGSU LEOCH BATTERY Co.,Ltd. Assignor: Shenzhen Leoch Power Technology Co.,Ltd. Contract record no.: 2010320000168 Denomination of invention: Nanometer-level high composite electrolyte and its preparing method Granted publication date: 20090429 License type: Exclusive License Record date: 20100308 |
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Address after: 1401, block a, building 6, Zhonggang Plaza, exhibition Bay, 83 ZHANJING Road, Heping community, Fuhai street, Bao'an District, Shenzhen, Guangdong 518000 Patentee after: Shenzhen Lishi New Energy Development Co.,Ltd. Address before: 518052, Shenzhen, Baoan District, Guanlan Town, Guangdong, village of the same rich industrial zone 9 Patentee before: Shenzhen Leoch Power Technology Co.,Ltd. |
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