CN106410288A - Colloid storage battery electrolyte and preparation method thereof - Google Patents
Colloid storage battery electrolyte and preparation method thereof Download PDFInfo
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- CN106410288A CN106410288A CN201610530873.2A CN201610530873A CN106410288A CN 106410288 A CN106410288 A CN 106410288A CN 201610530873 A CN201610530873 A CN 201610530873A CN 106410288 A CN106410288 A CN 106410288A
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- storage battery
- colloid storage
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
- H01M10/10—Immobilising of electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Manufacturing & Machinery (AREA)
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- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a colloid storage battery electrolyte and a preparation method thereof, and belongs to the technical field of colloid storage batteries. Polyvinylpyrrolidone is taken as a colloid stabilizer, lithium sulfate is taken as an additive and a phosphoric acid is taken as an auxiliary electrolyte; and performance test is carried out on the electrolyte by changing the content of various components to find out the most appropriate proportions: the polyvinylpyrrolidone accounts for 0.12% of total mass of the colloid storage battery electrolyte, the lithium sulfate accounts for 0.8% of total mass of the colloid storage battery electrolyte and the phosphoric acid accounts for 0.9% of total mass of the colloid storage battery electrolyte. The disadvantage of relatively high internal resistance of the colloid battery is improved, the capacity of the battery is improved and the service life of the battery is prolonged.
Description
Technical field
The invention belongs to the technical field of colloid storage battery, particularly to the production technical field of colloid storage battery electrolyte.
Background technology
Gelled lead acid battery is a kind of novel battery growing up on the basis of traditional lead-acid accumulator, also known as " maintenance-free battery ".Conventional colloid storage battery electrolyte forms：Aerosil accounts for the 4～6% of colloid storage battery electrolyte gross mass, and sulfuric acid accounts for the 36～40% of colloid storage battery electrolyte gross mass, and remaining is deionized water.
Compared with other lead-acid accumulators, main difference is electrolyte to gelled lead acid battery.Add gel in the electrolyte of colloid storage battery, when aerosil is dispersed in sulfuric acid solution, be easily connected with each other with hydrogen bond between independent silicone hydroxyl, form three-dimensional net structure, wrap up sulfuric acid and water, formed immobilising gel, be not in the situation of electrolyte stratification.And have gap in gel structure, ion can be made to pass freely through, to ensure the normal discharge and recharge of battery.
Colloid battery is that quasi- pregnant solution type designs it is ensured that preferable deep discharge recovery characteristics, effectively prevent the generation of electrolyte dry-out phenomenon.The passage that oxygen is combined being provided after colloidal electrolyte gel, and the colloidal electrolyte after gel has certain intensity, resistance when making gas escape is bigger, promoting gas to pass through gap in negative pole composite reduction, thus reducing the effusion of gas.The safe environmental protection again of colloid battery.Nowadays the safety and environmental protection consciousness more and more higher of people, not only considers the performance of battery, and focuses on the security of battery, the feature of environmental protection when selecting battery.Colloidal electrolyte can prevent dendrite short circuit；Little moisture loss, non-maintaining, there is no thermal runaway phenomenon；Acid mist is few, acid nonleakage, even if battery case has fine crack, battery also can normal work, transportation safety is convenient.
But, gelled lead acid battery also has itself significant shortcoming, and the internal resistance of such as gelled lead acid battery is relatively large, and capacity is less.Suitable deflocculant is added in colloidal electrolyte, additive and help electrolyte, it is excessive to improve its internal resistance, the less shortcoming of capacity.Therefore, suitable deflocculant, additive and help electrolyte to be the main path improving colloid battery performance are added.The deflocculant that the electrolyte prescription that the patent of Application No. 201410207589.2 provides uses is polyacrylamide.
Content of the invention
It is an object of the invention to provide one kind makes colloid battery internal resistance less, the bigger colloid storage battery electrolyte of capacity.
The present invention includes aerosil, sulfuric acid and deionized water, also includes polyvinylpyrrolidone, lithium sulfate and phosphoric acid.
It is deflocculant that the present invention adopts polyvinylpyrrolidone, and lithium sulfate is additive, and phosphoric acid is to help electrolyte, by experimental results demonstrate polyvinylpyrrolidone compared with polyacrylamide stabilizing effect more preferably, make electrolyte long-time place not stratified.The addition of lithium sulfate makes the internal resistance of battery reduce, and the addition of phosphoric acid then extends the service life of battery.Add in the electrolytic solution and help electrolyte phosphoric acid, the addition of phosphoric acid can reduce positive active material PbO2Softening rate, reduce it and come off moreover it is possible to mitigate the self discharge of battery, thus improving the cycle life of colloid battery.
Further, polyvinylpyrrolidone of the present invention, lithium sulfate and phosphoric acid account for 0.04～0.16%, 0.4～1.6% and the 0.3～1.2% of colloid storage battery electrolyte gross mass respectively.The electrolyte made by the addition of each composition above, can make that the internal resistance of colloid storage battery is less, and capacity is bigger, to improve the performance of battery.And stabilizer, additive and help electrolyte consumption few, low cost, preparation is simple, has higher feasibility.
When polyvinylpyrrolidone accounts for the 0.12% of colloid storage battery electrolyte gross mass, the colloid storage battery internal resistance that electrolyte is prepared is less.
When lithium sulfate accounts for the 0.8% of colloid storage battery electrolyte gross mass, the colloid storage battery internal resistance that electrolyte is prepared is less, and capacity is larger.
When phosphoric acid accounts for the 0.9% of colloid storage battery electrolyte gross mass, the colloid storage battery internal resistance that electrolyte is prepared is less, and capacity is larger.
It is another object of the present invention to proposing the preparation method of above colloid storage battery electrolyte.
Method is as follows：Aerosil is disperseed in deionized water, to be made into the aerosil hydrosol.Then, add the sulfuric acid solution of chilled process in the aerosil hydrosol, be sufficiently mixed.Then successively polyvinylpyrrolidone, lithium sulfate and phosphoric acid are added in mixed liquor again, be thoroughly mixed, form colloid storage battery electrolyte.
The present invention prepares electrolyte process is simple, and process stabilization is controlled, with low cost, the colloid battery applied range prepared using this electrolyte.
Brief description
Fig. 1 is the AC impedance figure of colloidal electrolyte of the present invention and existing colloidal electrolyte.
Fig. 2 is the cyclic voltammogram of colloidal electrolyte of the present invention and existing colloidal electrolyte.
Specific embodiments
First, prepare the example of colloidal electrolyte：
Embodiment 1：
Weigh 12.48mL water in 50mL small beaker, and weigh 1.8791g aerosil and add in small beaker, be made into the aerosil hydrosol（Carry out ultrasonic if necessary）.98% concentrated sulfuric acid deionized water is diluted to the aqueous sulfuric acid that proportion is 1.37, standing allows to cool to room temperature and carries out freezing processing.The aqueous sulfuric acid that 20mL proportion is 1.37 adds in the aerosil hydrosol being made into, and is sufficiently mixed.Weigh account for colloid storage battery electrolyte gross mass 0.04% polyvinylpyrrolidone, add in above-mentioned mixed liquor, be thoroughly mixed, make colloid storage battery electrolyte.
Embodiment 2：
Weigh 12.48mL water in 50mL small beaker, and weigh 1.8791g aerosil and add in small beaker, be made into the aerosil hydrosol（Carry out ultrasonic if necessary）.98% concentrated sulfuric acid deionized water is diluted to the aqueous sulfuric acid that proportion is 1.37, standing allows to cool to room temperature and carries out freezing processing.The aqueous sulfuric acid that 20mL proportion is 1.37 adds in the aerosil hydrosol being made into, and is sufficiently mixed.Weigh account for colloid storage battery electrolyte gross mass 0.08% polyvinylpyrrolidone, add in above-mentioned mixed liquor, be thoroughly mixed, make colloid storage battery electrolyte.
Embodiment 3：
Weigh 12.48ml water in 50ml small beaker, and weigh 1.8791g aerosil and add in small beaker, be made into the aerosil hydrosol（Carry out ultrasonic if necessary）.98% concentrated sulfuric acid deionized water is diluted to the aqueous sulfuric acid that proportion is 1.37, standing allows to cool to room temperature and carries out freezing processing.The aqueous sulfuric acid that 20ml proportion is 1.37 adds in the aerosil hydrosol being made into, and is sufficiently mixed.Weigh account for colloid storage battery electrolyte gross mass 0.12% polyvinylpyrrolidone, add in above-mentioned mixed liquor, be thoroughly mixed, make colloid storage battery electrolyte.
Embodiment 4：
Weigh 12.48mL water in 50mL small beaker, and weigh 1.8791g aerosil and add in small beaker, be made into the aerosil hydrosol（Carry out ultrasonic if necessary）.98% concentrated sulfuric acid deionized water is diluted to the aqueous sulfuric acid that proportion is 1.37, standing allows to cool to room temperature and carries out freezing processing.The aqueous sulfuric acid that 20mL proportion is 1.37 adds in the aerosil hydrosol being made into, and is sufficiently mixed.Weigh account for colloid storage battery electrolyte gross mass 0.16% polyvinylpyrrolidone, add in above-mentioned mixed liquor, be thoroughly mixed, make colloid storage battery electrolyte.
Drawn by embodiment 1～4：When the polyvinylpyrrolidone weighing accounts for the 0.12% of colloid storage battery electrolyte gross mass, the colloid storage battery internal resistance prepared by this electrolyte is less.
Embodiment 5：
Weigh 12.48mL water in 50mL small beaker, and weigh 1.8791g aerosil and add in small beaker, be made into the aerosil hydrosol（Carry out ultrasonic if necessary）.98% concentrated sulfuric acid deionized water is diluted to the aqueous sulfuric acid that proportion is 1.37, standing allows to cool to room temperature and carries out freezing processing.The aqueous sulfuric acid that 20mL proportion is 1.37 adds in the aerosil hydrosol being made into, and is sufficiently mixed.Weigh account for colloid storage battery electrolyte gross mass 0.12% polyvinylpyrrolidone, account for the 0.4% of colloid storage battery electrolyte gross mass lithium sulfate, add in above-mentioned mixed liquor, be thoroughly mixed, make colloid storage battery electrolyte.
Embodiment 6：
Weigh 12.48mL water in 50mL small beaker, and weigh 1.8791g aerosil and add in small beaker, be made into the aerosil hydrosol（Carry out ultrasonic if necessary）.98% concentrated sulfuric acid deionized water is diluted to the aqueous sulfuric acid that proportion is 1.37, standing allows to cool to room temperature and carries out freezing processing.The aqueous sulfuric acid that 20mL proportion is 1.37 adds in the aerosil hydrosol being made into, and is sufficiently mixed.Weigh account for colloid storage battery electrolyte gross mass 0.12% polyvinylpyrrolidone, account for the 0.8% of colloid storage battery electrolyte gross mass lithium sulfate, add in above-mentioned mixed liquor, be thoroughly mixed, make colloid storage battery electrolyte.
Embodiment 7：
Weigh 12.48mL water in 50mL small beaker, and weigh 1.8791g aerosil and add in small beaker, be made into the aerosil hydrosol（Carry out ultrasonic if necessary）.98% concentrated sulfuric acid deionized water is diluted to the aqueous sulfuric acid that proportion is 1.37, standing allows to cool to room temperature and carries out freezing processing.The aqueous sulfuric acid that 20mL proportion is 1.37 adds in the aerosil hydrosol being made into, and is sufficiently mixed.Weigh account for colloid storage battery electrolyte gross mass 0.12% polyvinylpyrrolidone, account for the 1.2% of colloid storage battery electrolyte gross mass lithium sulfate, add in above-mentioned mixed liquor, be thoroughly mixed, make colloid storage battery electrolyte.
Embodiment 8：
Weigh 12.48mL water in 50mL small beaker, and weigh 1.8791g aerosil and add in small beaker, be made into the aerosil hydrosol（Carry out ultrasonic if necessary）.98% concentrated sulfuric acid deionized water is diluted to the aqueous sulfuric acid that proportion is 1.37, standing allows to cool to room temperature and carries out freezing processing.The aqueous sulfuric acid that 20mL proportion is 1.37 adds in the aerosil hydrosol being made into, and is sufficiently mixed.Weigh account for colloid storage battery electrolyte gross mass 0.12% polyvinylpyrrolidone, account for the 1.6% of colloid storage battery electrolyte gross mass lithium sulfate, add in above-mentioned mixed liquor, be thoroughly mixed, make colloid storage battery electrolyte.
Drawn by embodiment 5～8：When the lithium sulfate weighing accounts for the 0.8% of colloid storage battery electrolyte gross mass, the colloid storage battery internal resistance prepared by this electrolyte is less, and capacity is larger.
Embodiment 9：
Weigh 12.48mL water in 50mL small beaker, and weigh 1.8791g aerosil and add in small beaker, be made into the aerosil hydrosol（Carry out ultrasonic if necessary）.98% concentrated sulfuric acid deionized water is diluted to the aqueous sulfuric acid that proportion is 1.37, standing allows to cool to room temperature and carries out freezing processing.The aqueous sulfuric acid that 20mL proportion is 1.37 adds in the aerosil hydrosol being made into, and is sufficiently mixed.Weigh account for colloid storage battery electrolyte gross mass 0.12% polyvinylpyrrolidone, account for the 0.8% of colloid storage battery electrolyte gross mass lithium sulfate, account for the 0.3% of colloid storage battery electrolyte gross mass phosphoric acid, add in above-mentioned mixed liquor, it is thoroughly mixed, make colloid storage battery electrolyte.
Embodiment 10：
Weigh 12.48mL water in 50mL small beaker, and weigh 1.8791g aerosil and add in small beaker, be made into the aerosil hydrosol（Carry out ultrasonic if necessary）.98% concentrated sulfuric acid deionized water is diluted to the aqueous sulfuric acid that proportion is 1.37, standing allows to cool to room temperature and carries out freezing processing.The aqueous sulfuric acid that 20mL proportion is 1.37 adds in the aerosil hydrosol being made into, and is sufficiently mixed.Weigh account for colloid storage battery electrolyte gross mass 0.12% polyvinylpyrrolidone, account for the 0.8% of colloid storage battery electrolyte gross mass lithium sulfate, account for the 0.6% of colloid storage battery electrolyte gross mass phosphoric acid, add in above-mentioned mixed liquor, it is thoroughly mixed, make colloid storage battery electrolyte.
Embodiment 11：
Weigh 12.48mL water in 50mL small beaker, and weigh 1.8791g aerosil and add in small beaker, be made into the aerosil hydrosol（Carry out ultrasonic if necessary）.98% concentrated sulfuric acid deionized water is diluted to the aqueous sulfuric acid that proportion is 1.37, standing allows to cool to room temperature and carries out freezing processing.The aqueous sulfuric acid that 20mL proportion is 1.37 adds in the aerosil hydrosol being made into, and is sufficiently mixed.Weigh account for colloid storage battery electrolyte gross mass 0.12% polyvinylpyrrolidone, account for the 0.8% of colloid storage battery electrolyte gross mass lithium sulfate, account for the 0.9% of colloid storage battery electrolyte gross mass phosphoric acid, add in above-mentioned mixed liquor, it is thoroughly mixed, make colloid storage battery electrolyte.
Fig. 1 reflects the colloid storage battery electrolyte that embodiment 11 is made（In figure curve 1）With existing colloidal electrolyte（In figure curve 2）AC impedance figure.It will be seen from figure 1 that the impedance of the colloidal electrolyte prepared by embodiment 11 is less, also imply that the electrochemical reaction resistance of electrolyte is less.
Fig. 2 reflects the colloid storage battery electrolyte that embodiment 11 is made（In figure curve 1）With existing colloidal electrolyte（In figure curve 2）Cyclic voltammogram.From figure 2 it can be seen that the peak height of the colloidal electrolyte prepared by embodiment 11 and peak area are all big than existing colloidal electrolyte, illustrate that the colloidal electrolyte discharge current prepared and capacity are all big than existing colloidal electrolyte.
Embodiment 12：
Weigh 12.48mL water in 50mL small beaker, and weigh 1.8791g aerosil and add in small beaker, be made into the aerosil hydrosol（Carry out ultrasonic if necessary）.98% concentrated sulfuric acid deionized water is diluted to the aqueous sulfuric acid that proportion is 1.37, standing allows to cool to room temperature and carries out freezing processing.The aqueous sulfuric acid that 20mL proportion is 1.37 adds in the aerosil hydrosol being made into, and is sufficiently mixed.Weigh account for colloid storage battery electrolyte gross mass 0.12% polyvinylpyrrolidone, account for the 0.8% of colloid storage battery electrolyte gross mass lithium sulfate, account for the 1.2% of colloid storage battery electrolyte gross mass phosphoric acid, add in above-mentioned mixed liquor, it is thoroughly mixed, make colloid storage battery electrolyte.
Drawn by embodiment 9～12：When the phosphoric acid weighing accounts for the 0.9% of colloid storage battery electrolyte gross mass, the colloid storage battery internal resistance prepared by this electrolyte is less, and capacity is larger.
Claims (6)
1. a kind of colloid storage battery electrolyte, including aerosil, sulfuric acid and deionized water it is characterised in that also including polyvinylpyrrolidone, lithium sulfate and phosphoric acid.
2. according to claim 1 colloid storage battery electrolyte it is characterised in that described polyvinylpyrrolidone, lithium sulfate and phosphoric acid account for 0.04～0.16%, 0.4～1.6% and the 0.3～1.2% of colloid storage battery electrolyte gross mass respectively.
3. according to claim 2 colloid storage battery electrolyte it is characterised in that described polyvinylpyrrolidone, lithium sulfate and phosphoric acid account for 0.12%, 0.8% and the 0.9% of colloid storage battery electrolyte gross mass respectively.
4. colloid storage battery electrolyte as claimed in claim 1 preparation method it is characterised in that：Aerosil is disperseed in deionized water, to be made into the aerosil hydrosol；Then, add in the aerosil hydrosol chilled process after sulfuric acid solution, after being sufficiently mixed, then polyvinylpyrrolidone, lithium sulfate and phosphoric acid will be added, agitated mix, obtain colloid storage battery electrolyte.
5. according to claim 4 colloid storage battery electrolyte preparation method it is characterised in that：The quality that feeds intake of described polyvinylpyrrolidone, lithium sulfate and phosphoric acid accounts for 0.04～0.16%, 0.4～1.6% and the 0.3～1.2% of colloid storage battery electrolyte gross mass respectively.
6. according to claim 5 colloid storage battery electrolyte preparation method it is characterised in that：The quality that feeds intake of described polyvinylpyrrolidone, lithium sulfate and phosphoric acid accounts for 0.12%, 0.8% and the 0.9% of colloid storage battery electrolyte gross mass respectively.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107579286A (en) * | 2017-08-29 | 2018-01-12 | 东莞恒量新能源科技有限公司 | A kind of mixed poly- additive of lead accumulator and preparation method thereof |
| CN108987824A (en) * | 2018-07-25 | 2018-12-11 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of the electrolyte of gelled lead acid battery |
| CN113285126A (en) * | 2021-04-13 | 2021-08-20 | 中国电力科学研究院有限公司 | Colloidal electrolyte and preparation method thereof |
| US20220200060A1 (en) * | 2020-12-18 | 2022-06-23 | Vesselin Bojidarov NAYDENOV | Synthetic proton-conductive additives for battery electrolytes |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107579286A (en) * | 2017-08-29 | 2018-01-12 | 东莞恒量新能源科技有限公司 | A kind of mixed poly- additive of lead accumulator and preparation method thereof |
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