CN106654392A - Electrolyte additive of lead-acid storage battery and preparation method for electrolyte additive - Google Patents
Electrolyte additive of lead-acid storage battery and preparation method for electrolyte additive Download PDFInfo
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- CN106654392A CN106654392A CN201611109907.7A CN201611109907A CN106654392A CN 106654392 A CN106654392 A CN 106654392A CN 201611109907 A CN201611109907 A CN 201611109907A CN 106654392 A CN106654392 A CN 106654392A
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- sulfate
- lead
- electrolyte
- electrolyte additive
- acid accumulator
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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
-
- 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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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to an electrolyte of a lead-acid storage battery, particularly to an electrolyte additive of the lead-acid storage battery; the electrolyte additive of the lead-acid storage battery can improve electrochemical performance, prolong the cycle life and improve capacity of the battery. The additive is prepared from graphene oxide, silicon dioxide, sulfate, stannous sulfate and EDTA-Na. By virtue of the electrolyte additive, the electrochemical performance and the capacity of the battery can be effectively improved and the cycle life of the lead-acid storage battery can be prolonged.
Description
Technical field
The present invention relates to lead-acid accumulator electrolyte, more particularly to one kind improves battery performance and improves circulating battery
Service life improves electrolyte additive for lead-acid accumulator of battery capacity and preparation method thereof simultaneously.
Background technology
When lead-acid accumulator connects circuit discharging, electronics is discharged by anode (negative plate), the Pb2+ ions of formation immediately with
SO42- ionic reactions, are deposited at the electrode surface insoluble lead sulfate.At negative electrode (positive plate), from the electricity of external circuit
PbO2 is reduced to water and Pb2+ ions by son, and Pb2+ ions react with sulfate ion immediately again, and PbS04 is deposited on electrode.
When battery discharges completely, negative electrode (positive plate) and anode (negative plate) be transformed substantially into PbSO4 (Gu).Battery is additional anti-
To voltage, there is reversible electrochemical reaction, i.e. battery and charge.During overcharge, positive plate generates thick titanium dioxide lead layer and releases
Oxygen is put, negative plate forms biscuit lead layer and release hydrogen.
For the purpose of to eliminate lead-acid accumulator sulfation, and then accumulator capacity and prolonging service life of battery are improved, just
After discharge, the active material on positive/negative plate is changed into the little crystallization of soft lead sulfate to normal battery, is evenly distributed in pole plate
In, it is easy to recover original brown lead oxide and spongy lead when charging, this is a kind of normal sulfation.Due to
Battery Slurry pump, can all cause irreversible (can not the recharge) sulfation of pole plate.Due to forming thick sulfuric acid on pole plate
Lead is crystallized, and can block the micropore of pole plate and dividing plate, hinders the osmosis of electrolyte, increased resistance, is difficult when charging extensive
Become spongy lead again, reduce the active material that electrochemical reaction is participated in pole plate, therefore capacity is seriously reduced, the lost of life.
Polar plate sulfation is the one of the main reasons of waste lead-acid accumulators.
Lead-acid accumulator typically adopts lead-antimony alloy as grid, but the presence and migration of antimony reduce lead-acid storage battery negative
Pole overpotential of hydrogen evolution, increases negative pole hydrogen-separating quantity.To improve lead-acid battery negative pole active substance conduction and charge acceptance
Etc. performance, acetylene black, activated carbon etc. are often added in negative plate reduces the material of overpotential of hydrogen evolution.
Traditional formula of lead-acid storage battery negative pole diachylon is lead powder, sulfuric acid, water and lignin, humic acid, barium sulfate, acetylene
It is black to wait swelling agent to mix in certain proportion.The lead carbon battery and superbattery of simultaneously new development in recent years is by by different content
Carbon doping improve its electric conductivity in cathode lead plaster, to improve the capacity of battery, extend service life of lead accumulator, reach height
Purpose with good circulation performance under multiplying power.But the doping of carbon will make the overpotential of hydrogen evolution of lead negative pole shuffle, and overcharge
It is possible to separate out substantial amounts of hydrogen when electricity and large current charge, increases water consume, increases the possibility that the unsafe incidents such as blast occur.Store
Battery after 90% lead sulfate is reduced to active material spongy lead, begins with hydrogen and separates out in charging process, but
When the low impurity of overpotential of hydrogen is there are on electrolyte or negative electrode active material, separate out in advance after hydrogen, make the hydrogen of battery
Amount of precipitation steeply rises.
A kind of entitled lead-acid accumulators of the A of CN 104064816 suppress electrolysis additive of liberation of hydrogen and preparation method thereof,
Including by poly-aspartic-acid, sulfate, butanedioic acid, disodium ethylene diamine tetraacetate, by the suction-operated of butanedioic acid and poly-
Asparatate refines the effect of crystal, improves negative acid accumulator negative pole overpotential of hydrogen evolution, improves battery performance raising
The lead-acid accumulator of circulating battery service life suppresses liberation of hydrogen electrolysis additive.It is disadvantageous in that, using the additive
Obtained cycle life of lead-acid accumulator is low, and capacitance is low.
The content of the invention
It is an object of the invention in order to solve in lifting of the existing electrolyte additive for lead-acid accumulator to cycle life
The low defect of poor, capacitance provides a kind of electrolyte additive for lead-acid accumulator and preparation method thereof.
To achieve these goals, the present invention is employed the following technical solutions：
A kind of electrolyte additive for lead-acid accumulator, it is characterised in that the additive is by graphene oxide, silica, sulphur
Hydrochlorate, stannous sulfate and EDTA-Na composition, in every liter of lead-acid accumulator electrolyte containing graphene oxide 200-300mg/L, two
Silica 1000-2000mg/L, sulfate 800-1500mg/L, stannous sulfate 2000-3000mg/L, EDTA-Na2000-
3000mg/L, balance of sulfuric acid solution；The density of the sulfuric acid solution is 1.05-1.4g/cm3。
The silica is nano silicon.
The sulfate be aluminum sulfate, copper sulphate, magnesium sulfate, chromium sulfate, cobaltous sulfate, nickel sulfate, barium sulfate, potassium sulfate,
One kind in sodium sulphate.
A kind of preparation method of described electrolyte additive for lead-acid accumulator is to add pure water in concentrated sulfuric acid by density
Adjust to 1.05-1.4g/cm3, dilute sulfuric acid is prepared into, take 1L dilute sulfuric acids and be heated to 45-50 DEG C, add the silica of formula ratio
After being well mixed, graphene oxide, sulfate, the stannous sulfate of formula ratio is added, EDTA-Na is then added while stirring, and
Stirred after 40-50min under 3000rmv/min rotating speeds with homogenizer, be cooled to after room temperature and continue high-speed stirred to mixing
Uniformly.
The beneficial effect that the present invention is reached：
The graphene oxide that the present invention is adopted increased the electric conductivity of electrolyte, can suppress solvent in the electrolyte of part point
Solution, reduces the impedance of battery, hence it is evident that improve the specific capacity and cyclical stability of battery；During lead acid storage battery tank discharge, positive pole
Active material on plate is converted into lead sulfate crystallization, newly-generated lead sulfate crystallization can on the preferential nucleus for generating not medium well
Long, the graphene oxide of addition can form absorption on sulfuric acid leading crystal, prevent sulfuric acid leading crystal from growing up, with new lead sulfate
Nucleus is continuously generated, and forms tiny sulfuric acid leading crystal, is conducive to diffusion of the sulfuric acid electrolyte in active material, makes participation electricity
The active matter quality of chemical reaction increases, and so as to improve battery capacity, improves charge acceptance, improves circulating battery and uses the longevity
Life；Simultaneous oxidation Graphene has the effect of absorption sulfuric acid, and improving discharging product makes it generate while PbSO4 is generated
PbSiO3, makes easily to be dissolved in sulfuric acid containing PbSiO3 in PbSO4 crystallizations, the precipitation of PbSO4 crystal is reduced, so as to improve electricity
Pond cycle life.There is coordination in graphene oxide, can effectively prevent stannous sulfate from existing in sulfuric acid solution with stannous sulfate
Decompose in water, producing precipitation affects battery performance, stannous sulfate is evenly dispersed in electrolyte, the Sn in charging process2+
Ion precipitation increases electric conductivity to negative plate Surface Creation metallic tin, so as to improve charge acceptance, and while improves appearance
Amount.
The nano silicon that the present invention is added forms in the electrolytic solution acid silicon dioxide sol, in the process of discharge and recharge
The middle lead electrode surface that can adsorb, in electrode surface network structure is formed, and makes hydrogen generate neutrality from being not readily available electronics
Hydrogen molecule, equivalent to improve hydrogen deposition potential, it is possible to reduce the precipitation of hydrogen.Under the conditions of larger multiplying power discharging, acid two
Silica effect in the electrolytic solution is to speed up mass transfer in liquid phase process, due to the presence of graphene oxide, the two uniform distribution
In battery liquid, can effectively improve the conductive capability of the final ion of electric discharge, be conducive to the further of active material
Using the increase with battery capacity, acid accumulator negative pole lead overpotential of hydrogen evolution is improved, improve battery performance and improve battery
Service life cycle.
Metal ion in the addition complexing electrolyte of EDTA-Na, generates metallic ion coordination compound in the present invention, but
The compound for being formed in acid condition is unstable, is easy to be reduced to metal when charging, lead sulfate crystallization after multiple discharge and recharge
Content is gradually decreased, and so as to improve battery performance circulating battery service life is improved；But the presence of iron tramp meeting exists
The both positive and negative polarity of battery forms respectively micro cell, and the active material for making both positive and negative polarity is constantly oxidized reduction, generates fine and close sulfuric acid
Lead is crystallized, and causes accumulator capacity to decline, and EDTA-Na can form stable complex compound with iron ion free in electrolyte,
So as to reduce the content of iron tramp, while solving the problems, such as self-discharge of battery, the performance of lead-acid accumulator is improve；Oxidation
There is coordination in Graphene and stannous sulfate, cause its cannot stable existence, after adding EDTA-Na, graphite oxide can be made
Alkene is uniformly dispersed in electrolyte, so as to improve battery performance.
Each material mixes according to a certain percentage as electrolysis additive in the present invention, improves battery performance,
Lead-acid accumulator circulation physical life is improve, and improves the capacitance of battery.
Specific embodiment
In order to further appreciate that the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Restriction.
Embodiment 1
A kind of preparation method of electrolyte additive for lead-acid accumulator, adds in concentrated sulfuric acid pure water by Auto-regulating System of Density of Heavy Medium to 1.05g/
cm3, dilute sulfuric acid is prepared into, take 1L dilute sulfuric acids and be heated to 45 DEG C, after adding nano silicon to be well mixed, add graphite oxide
Alkene, potassium sulfate, stannous sulfate, then add while stirring EDTA-Na, and are stirred under 3000rmv/min with homogenizer
40min, is cooled to after room temperature and continues high-speed stirred to being well mixed.Graphene oxide in wherein every liter lead-acid accumulator electrolyte
200mg/L, nano silicon 1000mg/L, potassium sulfate 800mg/L, stannous sulfate 3000mg/L, EDTA-Na2000mg/L,
Balance of sulfuric acid solution.
Embodiment 2
A kind of preparation method of electrolyte additive for lead-acid accumulator, adds in concentrated sulfuric acid pure water by Auto-regulating System of Density of Heavy Medium to 1.20g/
cm3, dilute sulfuric acid is prepared into, take 1L dilute sulfuric acids and be heated to 50 DEG C, after adding nano silicon to be well mixed, add graphite oxide
Alkene, potassium sulfate, stannous sulfate, then add while stirring EDTA-Na, and with homogenizer under 3000rmv/min rotating speeds
Stirring 45min, is cooled to after room temperature and continues high-speed stirred to being well mixed.Stone is aoxidized in wherein every liter lead-acid accumulator electrolyte
Black alkene 250mg/L, nano silicon 1100mg/L, potassium sulfate 1000mg/L, stannous sulfate 2500mg/L, EDTA-
Na2500mg/L, balance of sulfuric acid solution.
Embodiment 3
A kind of preparation method of electrolyte additive for lead-acid accumulator, adds in concentrated sulfuric acid pure water by Auto-regulating System of Density of Heavy Medium to 1.40g/
cm3, dilute sulfuric acid is prepared into, take 1L dilute sulfuric acids and be heated to 45 DEG C, after adding nano silicon to be well mixed, add graphite oxide
Alkene, potassium sulfate, stannous sulfate, then add while stirring EDTA-Na, and are stirred under 3000rmv/min with homogenizer
50min, is cooled to after room temperature and continues high-speed stirred to being well mixed.Graphene oxide in wherein every liter lead-acid accumulator electrolyte
300mg/L, nano silicon 2000mg/L, potassium sulfate 1500mg/L, stannous sulfate 2000mg/L, EDTA-Na3000mg/L,
Balance of sulfuric acid solution.
Comparative example：The lead-acid accumulator electrolyte of additive is not added.
The lead-acid accumulator electrolyte that embodiment 1-3 and comparative example are prepared is prepared into after 12V12Ah batteries to be carried out
Test.Specific experiment situation see the table below.
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Capacity | 12.9 | 12.9 | 12.8 | 12.5 |
| Life-span | 420 | 400 | 412 | 385 |
| Charge acceptance | 3.65 | 3.64 | 3.67 | 3.60 |
By the way that lead acid storage battery solution liquid obtained in each embodiment and comparative example to be prepared into the result tested after battery card
It is bright：Add what the cycle life that additive prepares lead-acid accumulator was not significantly larger than added, and its battery capacity, charging
Had by ability and greatly improved.
Potassium sulfate in embodiment 1 is substituted for into aluminum sulfate, copper sulphate, magnesium sulfate, chromium sulfate, cobaltous sulfate, nickel sulfate, sulphur
Any one in sour barium, potassium sulfate, sodium sulphate, by the lead-acid accumulator electrolyte for preparing 12V12Ah batteries are prepared into
After tested, Jing analyses find the result error of capacity, life-span, charge acceptance and the embodiment 1 of battery less, not shadow
Ring battery performance.
From result above：Additive provided by the present invention improves the battery capacity of lead-acid accumulator and charging
By ability, while substantially increasing the cycle life of lead-acid accumulator.
Embodiment described above is the preferably scheme in the present invention, and any pro forma limit is not made to the present invention
System, also has other variants and remodeling on the premise of without departing from the technical scheme described in claim.
Claims (4)
1. a kind of electrolyte additive for lead-acid accumulator, it is characterised in that the additive by graphene oxide, silica,
Sulfate, stannous sulfate and EDTA-Na composition, in every liter of lead-acid accumulator electrolyte containing graphene oxide 200-300mg/L,
Silica 1 000-2000mg/L, sulfate 800-1500mg/L, stannous sulfate 2000-3000mg/L, EDTA-Na2000-
3000mg/L, balance of sulfuric acid solution；The density of the sulfuric acid solution is 1.05-1.4g/cm3。
2. a kind of electrolyte additive for lead-acid accumulator according to claim 1, it is characterised in that the silica is
Nano silicon.
3. a kind of electrolyte additive for lead-acid accumulator according to claim 1, it is characterised in that the sulfate is sulphur
One kind in sour aluminium, copper sulphate, magnesium sulfate, chromium sulfate, cobaltous sulfate, nickel sulfate, barium sulfate, potassium sulfate, sodium sulphate.
4. a kind of preparation method of electrolyte additive for lead-acid accumulator, it is characterised in that add the pure water will be close in concentrated sulfuric acid
Degree is adjusted to 1.05-1.4g/cm3, dilute sulfuric acid is prepared into, take 1L dilute sulfuric acids and be heated to 45-50 DEG C, add the titanium dioxide of formula ratio
After silicon is well mixed, graphene oxide, sulfate, the stannous sulfate of formula ratio is added, EDTA-Na is then added while stirring,
And 40-50min is stirred under the rotating speed of 3000rmv/min with homogenizer, it is cooled to after room temperature and continues high-speed stirred to mixed
Close uniform.
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| CN201611109907.7A CN106654392A (en) | 2016-12-06 | 2016-12-06 | Electrolyte additive of lead-acid storage battery and preparation method for electrolyte additive |
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| CN201611109907.7A CN106654392A (en) | 2016-12-06 | 2016-12-06 | Electrolyte additive of lead-acid storage battery and preparation method for electrolyte additive |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107275674A (en) * | 2017-05-23 | 2017-10-20 | 天能电池(芜湖)有限公司 | A kind of combined electrolysis solution additive |
| CN107403964A (en) * | 2017-07-26 | 2017-11-28 | 合肥尚强电气科技有限公司 | Lead-acid storage battery electrolyte additive and preparation method thereof |
| CN108183266A (en) * | 2017-12-29 | 2018-06-19 | 北京峥程环保科技有限公司 | The agent of lead-acid accumulator Regeneration and Repair and method for restoring lead-acid battery |
| CN108258328A (en) * | 2017-11-13 | 2018-07-06 | 天能集团（河南）能源科技有限公司 | A kind of preparation method of colloidal electrolyte of lead acid accumulator |
| CN108933300A (en) * | 2017-05-22 | 2018-12-04 | 湖北润阳新能源有限公司 | A kind of energy storage colloidal electrolyte of lead acid accumulator |
| CN109037819A (en) * | 2018-07-24 | 2018-12-18 | 湖南欧翔科技有限公司 | A kind of battery refresh liquid, regeneration method and application |
| CN109103514A (en) * | 2018-08-22 | 2018-12-28 | 东莞市德东科技有限公司 | A kind of colloid electrolyte for lead-acid battery |
| CN110380137A (en) * | 2019-06-10 | 2019-10-25 | 吉林大学 | A kind of lead-acid battery electrolysis additive and preparation method thereof |
| CN111463484A (en) * | 2020-03-04 | 2020-07-28 | 国网湖北省电力有限公司孝感供电公司 | Recycling activated electrolyte for storage battery and manufacturing method thereof |
| CN111509309A (en) * | 2019-02-19 | 2020-08-07 | 广州纳为新材料科技有限公司 | Graphene-containing lead-acid battery repairing agent and preparation method thereof |
| CN112952209A (en) * | 2021-04-01 | 2021-06-11 | 华富(江苏)电源新技术有限公司 | Lead-acid storage battery, electrolyte thereof and preparation method of electrolyte |
| CN113437372A (en) * | 2021-06-21 | 2021-09-24 | 河南润祥能源科技有限公司 | Restoration method of retired lead-acid battery, restoration electrolyte and preparation method of restoration electrolyte |
| CN114583261A (en) * | 2022-03-10 | 2022-06-03 | 山东天润新能源材料有限公司 | Preparation and application of electrolyte of sodium ion secondary battery containing graphene oxide |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108933300A (en) * | 2017-05-22 | 2018-12-04 | 湖北润阳新能源有限公司 | A kind of energy storage colloidal electrolyte of lead acid accumulator |
| CN107275674A (en) * | 2017-05-23 | 2017-10-20 | 天能电池(芜湖)有限公司 | A kind of combined electrolysis solution additive |
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| CN109037819A (en) * | 2018-07-24 | 2018-12-18 | 湖南欧翔科技有限公司 | A kind of battery refresh liquid, regeneration method and application |
| CN109103514A (en) * | 2018-08-22 | 2018-12-28 | 东莞市德东科技有限公司 | A kind of colloid electrolyte for lead-acid battery |
| CN111509309A (en) * | 2019-02-19 | 2020-08-07 | 广州纳为新材料科技有限公司 | Graphene-containing lead-acid battery repairing agent and preparation method thereof |
| CN111509309B (en) * | 2019-02-19 | 2022-05-17 | 广州纳为新材料科技有限公司 | Graphene-containing lead-acid battery repairing agent and preparation method thereof |
| CN110380137B (en) * | 2019-06-10 | 2021-06-15 | 吉林大学 | Lead-acid storage battery electrolyte additive and preparation method thereof |
| CN110380137A (en) * | 2019-06-10 | 2019-10-25 | 吉林大学 | A kind of lead-acid battery electrolysis additive and preparation method thereof |
| CN111463484A (en) * | 2020-03-04 | 2020-07-28 | 国网湖北省电力有限公司孝感供电公司 | Recycling activated electrolyte for storage battery and manufacturing method thereof |
| CN112952209A (en) * | 2021-04-01 | 2021-06-11 | 华富(江苏)电源新技术有限公司 | Lead-acid storage battery, electrolyte thereof and preparation method of electrolyte |
| CN113437372A (en) * | 2021-06-21 | 2021-09-24 | 河南润祥能源科技有限公司 | Restoration method of retired lead-acid battery, restoration electrolyte and preparation method of restoration electrolyte |
| CN113437372B (en) * | 2021-06-21 | 2023-04-25 | 河南润祥能源科技有限公司 | Repairing method and electrolyte for retired lead-acid battery and preparation method of repairing method and electrolyte |
| CN114583261A (en) * | 2022-03-10 | 2022-06-03 | 山东天润新能源材料有限公司 | Preparation and application of electrolyte of sodium ion secondary battery containing graphene oxide |
| CN114583261B (en) * | 2022-03-10 | 2023-11-10 | 山东天润新能源材料有限公司 | Preparation method of sodium ion secondary battery electrolyte containing graphene oxide |
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Application publication date: 20170510 |