CN107565175A - A kind of two-phase compositions of lead accumulator and preparation method thereof - Google Patents
A kind of two-phase compositions of lead accumulator and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of two-phase compositions of lead accumulator and preparation method thereof, described two-phase compositions are combined by 10~90 parts by volume silicone compositions and 10~90 parts by volume silica mixed liquors；Silicone composition, which is based on 100 parts by volume, to be included：Main chain backbone is the parts by volume of siloxanes 2~15 of (Si O Si) structure；The parts by volume of organic silicon rubber 2~15；The parts by volume of methyl silicate 68~95.8；The parts by volume of polyvinyl alcohol 0.2~1；Silica mixed liquor, which is based on 100 parts by volume, to be included：The parts by volume of aerosil 5~15；The parts by volume of industrial pure water 83~94.8；The parts by volume of lauryl sodium sulfate 0.2~2；Described two-phase compositions are prepared by process of the present invention, and for mix sulphur acid solution, the anti-softening ability of positive active material can be strengthened by adding inside lead accumulator, help softening active material to recover hardening, addition is few, cost-effective.
Description
Technical field
The present invention relates to the field of material technology of lead accumulator, the two-phase compositions of more particularly to a kind of lead accumulator and
Its preparation method.
Background technology
In recent years energy storage market common requirements Large Copacity lead accumulator is made to match somebody with somebody and applied mechanically, but conventional lead accumulator uses table out of doors
Reveal short life, discarded rate is higher, constrains the business application of energy-storage system.Industry is generally accepted, in the sulfuric acid of lead accumulator
Liquid adds appropriate colloidal substance, can effectively lift the life-span used out of doors.The colloidal materials that lead accumulator tradition uses
For aerosil, in addition, in Chinese invention patent publication number CN1383225A, one kind is disclosed by poly- element organosilicon
The silicone composition of oxygen alkane, silicone oil and the mixing of positive silicic acid aqueous solution of ester, said composition mixes to gather with sulfuric acid liquid is used as lead accumulator
Electrolyte or forming liquid.Applied by ten several years, industry generally believes the electricity of aerosil colloid and organosilicon colloid
Chemical characteristic is each has something to recommend him, and silicon dioxide colloid and silicone composition, which are used in mixed way, can reach technical advantage complementation.
In the industry in material prescription development in recent years, it is intended to a kind of biodegradable vinyl polymeric materials of application,
But some are added into the method for vinyl polymeric materials and unsatisfactory, technology original in sulfuric acid liquid or in silicon dioxide colloid
Because：Polyvinyl is a kind of high polymer material, and it is difficult to obtain stable coupling to be added directly into aqueous phase system, and will
It is added into that the performance of the lead accumulator electrochemistry after sulfuric acid liquid is not good enough, for example, to the electro-chemical activity of lead accumulator, reduce internal resistance
Without contribution；In addition, some colloids have used some emulsifier, such as tween, Span series etc., this kind of breast for good dispersion
Though agent can be stablized fine dispersion system, impurity is belonged to lead accumulator.Therefore, industry wishes to seek to a kind of both real
Existing silicon dioxide colloid and silicone composition are stable to be coupled, and applies the two-phase of vinyl polymeric materials in fine dispersion system
Composition.
The content of the invention
It is an object of the invention to：For current lead accumulator in the market silicon dioxide colloid and silicone composition colloid
Technological deficiency, there is provided one kind not only can fully be coupled aerosil and silicone composition but also in the two-phase compositions
The two-phase compositions of polyvinyl are implanted into, the electro-chemical activity of lead accumulator can be strengthened by being allowed to be directly added into sulfuric acid liquid, be reached
To lifting charging and discharging capabilities, the technical goal of increasing storage battery service life.
To achieve the above object, the invention provides a kind of two-phase compositions of lead accumulator, the two-phase compositions base
In 100 parts by volume, combined by the silicone composition of 10~90 parts by volume and the silica mixed liquor of 10~90 parts by volume and
Into；Described silicone composition is based on 100 parts by volume, including following components and content：
Component A：Main chain backbone be (- Si-O-Si-) structure and side base containing more than one unsaturated hydrophilic active group R,
Molecular weight is less than 3000 siloxanes, 2~15 parts by volume；
B component：Viscosity is less than the organic silicon rubber of 1500 pas, 2~15 parts by volume；
Component C：10wt%-30wt% methyl silicate, 68~95.8 parts by volume；
D components：The water miscible parts by volume of polyvinyl alcohol 0.2~1, described water miscible polyvinyl alcohol are active matter content
8~10% fluid product；
Described silica mixed liquor is based on 100 parts by volume, including following components and content：
Aerosil：5~15 parts by volume；
Industrial pure water：83~94.8 parts by volume；
Lauryl sodium sulfate：0.2~2 parts by volume, described lauryl sodium sulfate are active matter content 30~40%
Fluid product.
In the content of above-mentioned aerosil, described parts by volume is the scaled value of its weight/proportion；
In the component of the two-phase compositions of above-mentioned lead accumulator, R contained by the component A siloxanes side base include H,
OH、SO2H、NH2、CH3Or other unsaturated hydrophilic active groups.
In the component of above-mentioned two-phase compositions, the organic silicon rubber of the B component includes methyl silicone rubber, ethyl silicon rubber
Glue, methyl phenyl silicone rubber, the organic silicon rubber containing nitrile silicone rubber or containing other organic groups.
In the component of above-mentioned two-phase compositions, the alkalescence that preparation process is used for regulation composition intermediate pH value is additionally included in
Regulator.Described alkaline regulator includes but is not limited to using sodium hydroxide, potassium hydroxide.
The material and ratio range of two-phase compositions based on above-mentioned lead accumulator, present invention also offers one kind by institute
The preparation method that stock is fabricated to the two-phase compositions of lead accumulator is stated, this method includes：
1) described component A and described B component are thoroughly mixed and uniformly, then add described component C, fully
It is uniformly mixed；
2) mixture obtained to step 1) adds described D components, is thoroughly mixed and uniformly, obtains described silica
Alkane composition；
3) described aerosil and described industrial pure water are uniformly mixed, are being thoroughly mixed process
The middle alkaline regulator described in adjusts the pH value of mixture to 8-10；
4) mixture obtained to step 3) adds described lauryl sodium sulfate, is thoroughly mixed uniformly, obtains
Described silica mixed liquor；
5) the silica mixed liquor that step 4) obtains and the silicone composition that step 2) obtains are matched somebody with somebody by the volume
It is well mixed than scope, that is, obtains two-phase compositions of the present invention.
Present invention also offers a kind of electrolyte of two-phase compositions containing lead accumulator described above or liquid is repaired,
Described electrolyte or reparation liquid is combined by described two-phase compositions with density for 1.05-1.35 conventional sulfuric acid liquid；
Volume content of the described two-phase compositions in the electrolyte is not less than 0.2%, the volume content in the reparation liquid
Not less than 2%.
In the present invention, the viscosity of the two-phase compositions made of the material prescription and preparation technology is low, is added into sulfuric acid
Gel is slow after liquid, is typically added into the technological requirement that sulfuric acid liquid a few hours still meet lead accumulator routine liquid filling, and versatility
It is good, it can be used in mixed way with other conventional additives of lead storage battery electrolytic solution.
Silicon dioxide colloid and silicone composition colloid have respective advantage and disadvantage, the sky of industrial gas aerosil
Between volume belong to non-type structure, when its average grain diameter is more than tens nanometer, produced inorganic colloid viscosity is big, filling
Manufacturability is poor, and it is low that the lead accumulator of supporting making shows as initial capacity；And if aforementioned silicone composition can not be fabricated to
Particle diameter is less than 10 nanometers of ball shape structure, although being added into, the organic colloid viscosity that sulfuric acid liquid is produced is small, filling process is good,
But the chemical property of supporting making lead accumulator is equally undesirable, such as lead accumulator latter stage capacity attenuation speed is relatively large.
Silicon dioxide colloid and silicone composition are fully coupled, silicon dioxide colloid is can reach and silicone composition has complementary advantages
Technical purpose.
Before have described, polyvinyl is a kind of high polymer material, is added directly into sulfuric acid liquid or silica
The aqueous phase system of colloid is difficult to obtain stable coupling；Water miscible polyvinyl alcohol is made in the present invention have selected polyvinyl
For the component of the two-phase compositions, and it is all the organic system of high polymer material by polyvinyl alcohol implantation, obtained two-phase
Composition is added into sulfuric acid liquid and can effectively lift the high current charge-discharge ability of lead accumulator, reduce internal resistance.Dodecyl sulphate
Sodium is a kind of good electrolyte activating agent, and its hydrophilic lipophilic balance (HLB) is 40, the hydrophilic group with fine dispersion performance
Surface-active, the coupling of silicon dioxide colloid and silicone composition can be promoted, so as to avoid using electricity such as tween, Span series
Change the impurity emulsifying agent of reaction, be effectively improved the electro-chemical activity of the two-phase compositions, lift the high current of two-phase compositions
Discharge capability and low temperature charging ability.
Described two-phase compositions, which add sulfuric acid liquid, has preferable percdation ability to positive electode of lead battery, slows down lead
Battery anode active substance lattice avalanche speed caused by lead sulfate oxidationreduction, positive-plate life is given extension, (lead stores
The major technique reason of battery end of life be positive material(PAM) softening caused by, account for end-of-life probability 80%), this
When two-phase compositions of the present invention can be considered a kind of for extending the life-span reinforcing agent that uses of positive pole；Similarly, when lead electric power storage
Pond because positive material(PAM) softening cause capacity attenuation when, now two-phase compositions of the present invention can be considered a kind of for just
The reparation solution additive of pole capacity reparation.
A kind of two-phase compositions of lead accumulator of the present invention and preparation method thereof advantage is：
The two-phase compositions produced with material prescription of the present invention and preparation method, can directly it add by a certain percentage
Sulfuric acid liquid is added, the polyvinyl alcohol and the lauryl sodium sulfate in inorganic phase addition that the two-phase compositions are implanted into organic phase,
Contribute to the electro-chemical activity of two combined fine dispersion systems lifting lead accumulators, be it is a kind of have to positive active material it is good
The two-phase compositions of good effect, using effect is good, and purposes is wide.
Embodiment
With reference to embodiment further to a kind of material of the two-phase compositions of lead accumulator of the present invention, match somebody with somebody
Side and its and its prepare process be described in detail.
Component A siloxanes of the present invention is one kind in macromolecule silicon compound, and its architectural feature is main chain backbone
Contain more than one unsaturation with m (- Si-O-Si-) segments, the positive integer of described m Wei≤1, its side base (side chain)
Hydrophilic active group R, wherein described R includes but is not limited to H, OH, SO2H、NH2、CH3Deng or other unsaturated parents
Water active group；In numerous main chain backbones in the siloxanes of (- Si-O-Si-) segmented structure, all side bases (side chain) contain insatiable hunger
It can select to be coupled with B component organic silicon rubber with the poly- element siloxanes of hydrophilic active group, to ensure component A and B groups
Divide and be easier to be coupled under normal conditions, and be easily diluted after being copolymerized with B component, the A groups that molecular weight should be selected to be less than 3000
Point.
A species in the organic silicon rubber category organosilicon material of the B component, its product line include methyl silicon rubber
Glue, ethyl silicon rubber, methyl phenyl silicone rubber, the organic silicon rubber containing nitrile silicone rubber or containing other organic groups, have different poly-
Right chain structure, with chain hop count n increases, molecular weight increases, and viscosity increases, and viscosity should be selected to be less than 1500 during application
The organic silicon rubber product of pa, such flowable organic silicon rubber are commonly called as liquid silastic；One of important function of B component,
It is the end-capping reagent of the molecular structure segment as component A.
Described component C is the 10wt%-30wt% methyl silicate aqueous solution, and the chemical formula of methyl silicate is
C4H12O4Si, it is good organic solvent and organic synthesis intermediate, there is both sexes coupling, the important function of component C
One of, be it is both easily full cross-linked with hydrophilic component A, again can be full cross-linked with oil loving B component, therefore component C
When being copolymerized with component A and B component, the scattered silicone combinations objects system evenly of differential is easily formed；A kind of two-phase interface is theoretical
Think, the special compound bone of the copolymerization formation of (A+B+C), the segmented structure after (A+B+C) copolymerization can be made in electrolyte system
Middle formation is more beneficial for the passage that ion cluster gathering closes directed movement, the ability of increase ion set transition in the channel, meanwhile,
This combined electrolysis plastidome is advantageous to the absorption electric double layer of the two-phase interface formation dynamic equilibrium of middle electrode and electrolyte, strengthens
The activation energy that ion reacts in electrode surface, accelerate the reaction speed of electrode, so as to strengthen the high current respond of electrode.
The polyvinyl alcohol (PVA) of the D components is a kind ofBeing uniquely can be by bacterium as carbon source and the energy
The polyvinyl utilized, belong to a kind of Biodegradable polymer material, while be a kind of great secondary development potentiality
It is excellentSuch as based on solwution method, thin-film material can be prepared by casting film-formingApplication of the lead accumulator industry to PVA
Viewpoint is concentrated mainly on water miscible polyvinyl alcohol, but polyvinyl alcohol is a kind of organic matter, and directly addition is in sulfuric acid liquid or gas phase
The chemical property of silica dispersion system is not good enough；Water miscible polyvinyl alcohol of the present invention be active matter content 8~
10% fluid product, it is organic phase system that it, which is implanted into the approach of additive package of the present invention, as organic phase system
Dispersant and emulsion stabilizer, stable sulfuric acid is being coupled and is being added into being played in the polymerizeing of fumed silica dispersion system
Strengthen the effect of activity after liquid.
Described aerosil (white carbon) is that a kind of colloid known to lead accumulator manufacturing prepares material, its
Chemical formula is SiO2, the concentrated phosphoric acid of hydrofluoric acid and heat is soluble in, bases and can be melted and worked；Aerosil because of particle diameter very
Small, specific surface area is big, and superficial attractive forces are strong, and surface energy is big, and chemical purity is high, and dispersive property is good, has in thermal resistance, resistance etc.
There is specific performance, be always lead accumulator manufacturing colloidal electrolyte with its superior stability, reinforcing and thixotropy
Traditional material.Due to aerosil impalpable structure and in foam-like is accumulated, easily floated by moving air, true volume
Difficult accurate measuring, therefore aerosil parts by volume of the present invention, recommend to use volume instead and with proportion multiply in practical operation
Long-pending parts by weight metering.
Described industrial pure water is also known as industrial water, deionized water etc., because common source water salt content and pH value not
Together, these trace impurities can influence the production effect of the two-phase compositions；Industrial pure water is routinely that source water is passed through into electrodialysis
Device method, ion-exchanger method, hyperfiltration and be made, industrial pure water of the present invention, the ion removed includes cation
And anion, technical requirements resistivity is more than 10 megohms.
Described lauryl sodium sulfate is also known as lauric alcohol (or laruyl alcohol) sodium sulphate, chemical formula C12H25SO4Na, it is one
Kind anion surfactant, soluble in water, its hydrophilic lipophilic balance (HLB) is 40, belongs to hydrophilic based surfactants, with
The multiple compatibility of anion, nonionic is good, has a good dispersive property, and industrial goods are white or flaxen micro- viscous thing, conventional
In detergent and textile industry, the active matter content of procurement of commodities is general all higher, and the active matter content of fluid product is general all
>=27%, it should be diluted through industrial pure water or other solvents during as dispersant.According to industry experience, disperse gas phase with industrial pure water
During silica, the dispersion effect that hydrophilic based surfactants are added in industrial pure water can be more preferable；Lauryl sodium sulfate is at this
Main function in invention combined additive formula, the both dispersion aids as aerosil, while be a kind of good again
Electrolyte activating agent.
The effect of the alkaline regulator is to adjust the pH value of preparation process intermediate, and its selection includes all achievable mixed
Compound intermediate pH value adjusts and will not produce the basic species of sediment, and it belongs to micro in the two-phase compositions, material choosing
Select wide, but consider from cost performance, preferably sodium hydroxide or potassium hydroxide.In combined additive preparation method of the present invention, use
Alkaline regulator adjusts the main function of the intermediate pH value, is that can make the aerosil aqueous solution in alkaline environment
Fine dispersion system is more stable.
Above-described raw material can be purchased commercially, and the purity requirement of the aerosil reaches
99.99%, the component A, B component, component C, D components and polyvinyl alcohol, the purity requirement of lauryl sodium sulfate are at least
Technical pure, more preferably, the contaminant overstandard of raw material influences whether the synthetic effect of the two-phase compositions to SILVER REAGENT, by contaminant overstandard
Two-phase compositions be added to the electrolyte of lead accumulator, lead accumulator increase self discharge can be caused or even produce other pairs and made
With, while the storage period of the two-phase compositions can be influenceed.
The two-phase compositions of lead accumulator of the present invention can not use one kettle way to mix, and be followed after need to stocking up certain
Prepared by process, the preparation method includes：
1) described component A and described B component are thoroughly mixed and uniformly, then add described component C, fully
It is uniformly mixed；
2) mixture obtained to step 1) adds described D components, is thoroughly mixed and uniformly, obtains described silica
Alkane composition；
3) described aerosil and described industrial pure water are uniformly mixed, are being thoroughly mixed process
The middle alkaline regulator described in adjusts the pH value of mixture to 8-10；
4) mixture obtained to step 3) adds described lauryl sodium sulfate, is thoroughly mixed uniformly, obtains
Described silica mixed liquor；
5) the silica mixed liquor that step 4) obtains and the silicone composition that step 2) obtains are matched somebody with somebody by the volume
It is well mixed than scope, that is, obtains two-phase compositions of the present invention.
Above-mentioned steps 1) and step 2) can form the preferable silicone combinations objects system of mobility in normal condition.
Above-mentioned steps 3) in operation, because of the more difficult accurate measuring of the actual volume of aerosil, use instead volume with than
The parts by weight metering of weight product is more convenient.The pH value of the aerosil aqueous solution is adjusted to 8-10, is in order that gas phase two
The degree of scatter of the silica aqueous solution is more stable, and step 4) is preferably coupled in the basic conditions.When step 3) is obtained
Mixture clarity deficiency (generally with apparent viscosity big), can also be by adjusting the ratio of aerosil and industrial pure water
Example adjusts clarity, makes the quality of mixture more preferably.
In order that the quality of the two-phase compositions is more preferable, can also continue to increase conventional filterer afterwards in step 5)
Skill.Described two-phase compositions, if desired for long-term storage or as commodity selling, can continue to fit after step 5) is completed to prepare
Amount adds alkaline regulator and adjusts its pH value to more than 10.
Being stirred in the preparation method can be carried out at normal temperatures and pressures, and described is stirred including rotatably stirring
Mix, the shearing stirring that periodicity or corner cut are random, can also heat, help reaction using compressive reaction kettle, such as in mixture
Be stirred during keep mixture temperature be 75 DEG C ± 15 DEG C；When adding reaction pressure to mix using reactor, kettle
Pressure is no more than 25MPa.
The two-phase compositions of lead accumulator of the present invention are a kind of typical micro- dispersoids, are successful journey
Degree associates larger with preparation method, and its production effect can be tested by Tyndall (Tyndall) phenomenon to colloidal dispersion；
It is known in industry, wavelength be 400-700mm light by microdispersed colloidal dispersion when, if dispersed colloidal particle is straight
Footpath, which is less than lambda1-wavelength, to be scattered, and current general experiment conclusion is：When colloidal dispersion system particle diameter≤
During 94nm, luminous intensity is hit in scattering and the biquadratic of wavelength is inversely proportional.The Tyndall phenomenon of prepared two-phase compositions is obvious, says
The making of bright two-phase compositions reaches Technology design target；Conversely, can verify made two-phase compositions system not into
Work(.
More deep personnel are studied for this area, completely can be by different component mixed to above-described preparation method
The regulation of conjunction process carries out equivalent substitution, but the change of preparation process condition easily produces isomers, influences whether finally to mix
Electrochemistry effect of thing.Different selections and the married operation that feeds intake, on the premise of final mixture is similar, there may be
The contradiction of clarity and electrochemistry effect, the latter are often related to the aobvious state degree of Tyndall phenomenon.When can'tting eat one's cake and have it, push away
Recommend electrochemistry effect preferably process for refining.
The two-phase compositions of lead accumulator of the present invention can be considered a kind of pervasive additive of electrolyte, by certain during use
Ratio directly makes an addition to sulfuric acid liquid, when mixed with other additives, it is necessary to the performance of lead-acid battery to using other additives with
Test, the mixtures' ratio with other additives is determined with cost performance.
Conventional sulfuric acid liquid is added into the two-phase compositions of lead accumulator of the present invention, filling lead accumulator has
The obvious technical advantage of following items：
1st, the coupling of inorganic aerosil and silicone composition is stable, is added into the sulfuric acid liquid tool of lead accumulator
The double technique advantage of standby aerosil colloid and silicone composition colloid；
2nd, after the combination colloidal additive is added to conventional sulfuric acid liquid, the life time decay of lead accumulator performance is more steady,
And lead accumulator can obtain increase capacity, reduce the income of internal resistance；
3rd, preferable anti-softening and capacity repairs effect to positive electode of lead battery active material.
4th, versatility is good：It can be used in mixed way with other conventional additives of lead accumulator；
5th, stability is good, adapts to storage, transports and sell the commodity turnaround time needed for each link.
Following examples are only used for further illustrating technical scheme, and these technical schemes can be used alone,
It can add or combine and use other mature technologies.
Embodiment 1
Design and a kind of add in lead accumulator sulfuric acid liquid, the two combined of the anti-softening ability of positive active material can be increased
Thing, the two-phase compositions are combined by the silicone composition of 70 parts by volume and the aerosil of 30 parts by volume, wherein,
In terms of 100 parts by volume, component and content are silicone composition：
Component A：There is the siloxanes of some (- Si-O-Si-) segmented structures using a kind of main chain backbone, its side base contains H,
Molecular weight 1200, addition are 15 parts by volume；
B component：Viscosity be 1000 pas methyl silicone rubber, 15 parts by volume；
Component C：10wt% methyl silicate, 69 parts by volume；
D components：Active matter content is the 8% water miscible parts by volume of polyvinyl alcohol liquid 1；
Described silica mixed liquor is based on 100 parts by volume, including following components and content：
Aerosil：5 parts by volume；
Industrial pure water：94.7 parts by volume；
Active matter content is 40% lauryl sodium sulfate fluid product：0.3 parts by volume.
In addition the sodium hydroxide of pH value adjustment is ready for, is prepared after completing stock with following process：
1) component A of 15 parts by volume and the B component of 15 parts by volume are thoroughly mixed uniformly, then add 69 volumes
The component C of part, it is thoroughly mixed uniformly；
2) mixture obtained to step 1) adds the D components of 1 parts by volume, is thoroughly mixed uniformly, obtains described
Silicone composition；
3) aerosil of 5 parts by volume is well mixed with the industrial pure water of 94.7 parts by volume, stirring 5 minutes, so
The pH value of mixture is adjusted to 8 with described sodium hydroxide afterwards, continues stirring 20 minutes；
4) mixture obtained to step 3) adds the lauryl sodium sulfate of 0.3 parts by volume, stirs 5 minutes, obtains institute
The silica mixed liquor stated；
5) on the basis of 30 parts by volume of mixture obtained by step 4), it is slowly added to the silica obtained by 70 parts by volume steps 2)
Alkane composition, is sufficiently stirred during being slowly added to, and two kinds of mixtures are well mixed, and the final mixture of gained is this
Two-phase compositions described in embodiment.
Above-mentioned preparation method is stirred at normal temperatures and pressures, and the two-phase compositions of gained need to such as be deposited for a long time, add in right amount
Described sodium hydroxide is added to adjust the pH value of the two-phase compositions to 11.
The two-phase compositions that the present embodiment obtains can be as a kind of wide spectrum additive of lead accumulator sulfuric acid liquid, according to not
Same purposes adds different proportion in the sulfuric acid liquid of lead accumulator.
Embodiment 2
Two-phase compositions that embodiment 1 is obtained and lead accumulator sulfuric acid liquid that density is 1.245 by volume 1：99 is mixed
Closing uniformly, turns into a kind of two-phase compositions of lead accumulator mixes poly- colloidal electrolyte with sulfuric acid liquid.
Colloidal electrolyte described in the present embodiment is filled into 2V500Ah energy storage to be stored with the lead of valve-regulated AGM diaphragm structures
Inside battery, after conventional dipping, formation charging, turn into a resistant to elevated temperatures extraordinary colloid plumbic storage battery.The two of the present embodiment
Combined thing is with volume ratio 1：The filling lead accumulator of 99 mix sulphur acid solutions uses, and under the liquid-tight degree same case of sulfuric acid, can make lead
The effect that battery substantially obtains and reduces internal resistance, increases capacity.
In the present embodiment, the conventional anhydrous sodium sulfate of lead accumulator industry can be also added in described colloidal electrolyte,
Anhydrous sodium sulfate accounts for the 0.35% of the extraordinary colloidal electrolyte volume total amount, and industry is generally accepted, and is added in colloidal electrolyte
The anhydrous sodium sulfate of certain content, electrolyte electrochemical activity can be lifted, reduces the internal resistance of colloid plumbic storage battery, lifts colloid
The charge acceptance of lead accumulator.
Embodiment 3
In embodiment 1, the volume proportion of described silicone composition and aerosil mixed liquor is 70：30, this
The volume proportion is changed into 30 by embodiment：70, remaining preparation method is same as Example 1.
Typically contrast effect test result on probation is：Silicone composition is different from the proportioning of aerosil, mixes
Different electrochemical properties can be shown by closing sulfuric acid liquid addition lead accumulator, when two-phase compositions are based on silicone composition
When, lead accumulator, which can obtain, reduces internal resistance, the income of increase capacity；And when increasing the mixed proportion of aerosil, lead
The cycle charge-discharge life time decay that battery is shown is more steady.
The two-phase compositions of the present embodiment are with volume ratio 1：The filling lead accumulator of 99 mix sulphur acid solutions uses, and can make lead electric power storage
The cycle charge discharge electric life in pond is better than the effect of embodiment 2.
Embodiment 4
Design a kind of electrolyte two-phase compositions for adapting to the lead accumulator that long-term floating charge system uses, the two-phase compositions by
The silicone composition of 10 parts by volume and the silica mixed liquor of 90 parts by volume combine, wherein, silicone composition with
100 parts by volume meters, component and content are：
Component A：Used siloxanes is that main chain backbone has some (- Si-O-Si-) segmented structures, and molecular weight is
1500, its side base contains SO2H, the parts by volume of addition 2；
B component：Viscosity be 1100 pas ethyl silicon rubber, 2 parts by volume；
Component C：30wt% methyl silicate, 95.8 parts by volume；
D components：Active matter content is the 10% water miscible parts by volume of polyvinyl alcohol liquid 0.2；
Described silica mixed liquor is based on 100 parts by volume, including following components and content：
Aerosil：15 parts by volume；
Industrial pure water：83 parts by volume；
Active matter content is 30% lauryl sodium sulfate fluid product：2 parts by volume.
In addition the potassium hydroxide of pH value adjustment is ready for, is prepared after completing stock with following process：
1) component A of 2 parts by volume and the B component of 2 parts by volume are thoroughly mixed uniformly, then add 95.8 volumes
The component C of part, it is thoroughly mixed uniformly；
2) mixture obtained to step 1) adds the D components of 0.2 parts by volume, is thoroughly mixed uniformly, obtains described
Silicone composition；
3) industrial pure water of 83 parts by volume is well mixed with the aerosil of 15 parts by volume, made in mixed process
The pH value of gained mixture is adjusted to 10 with alkaline regulator, and is pressurizeed and heated using reactor and help reaction, kettle pressure is
20MPa, it is 75 DEG C ± 10 DEG C that mixed process, which keeps the mixture temperature in kettle, is persistently stirred 25 minutes；In the step,
If mixture clarity deficiency or viscosity are bigger than normal, can also be adjusted by adjusting the ratio of industrial pure water and aerosil
The clarity of abridged edition step mixture；
4) mixture obtained to step 3) adds the lauryl sodium sulfate of 2 parts by volume, stirs 10 minutes, obtains described
Silica mixed liquor；
5) the step 3) reactor kettle pressure and mixture temperature under the conditions of, 90 parts by volume steps 4) are obtained two
Silica mixed liquor is slowly added to the silicone composition obtained by 10 parts by volume steps 2), is adding the process of silicone composition
In be sufficiently stirred, be well mixed, final mixture is the two-phase compositions described in the present embodiment；By the two-phase obtained by this step
Composition filters, and it is product to take filtrate.
Content of the present embodiment because of silica mixed liquor in two-phase compositions is higher, is made greatly with suitable after sulfuric acid liquid
Capacity lead accumulator, it is especially suitable for the outdoor energy storage lead accumulator for making long-term floating charge.
Embodiment 5
The two-phase compositions that embodiment 1 is obtained use the homogenizing processing of high-speed emulsifying machine, described high-speed emulsifying machine
Homogenizing rotary speed be more than 20000 revs/min, after the two-phase compositions homogenized deep processing processing, with the lead that density is 1.20
Electrolyte acid liquid by volume 1：9 mixing are uniformly dispersed, and turn into a kind of and repair the special of positive electode of lead battery active material
With additive, market is commonly called as repairing liquid or renovation agent.
The reparation liquid of the present embodiment is added into through being judged as positive material(PAM) softening and held by quantifying for 1ml/10Ah
Inside the lead accumulator for measuring decay, the inner panel group point through adding negative pressure technique to make the reparation liquid in lead accumulator known to industry
After cloth is uniform, by secondary formation charging technique known to industry, the positive plate active material of softening is hardened again, treat this
The positive plate active material of the lead accumulator of reparation recovers capacity again.
It should be noted last that the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted.Although ginseng
The present invention is described in detail according to embodiment, it will be understood by those within the art that, to the technical side of the present invention
Case is modified or equivalent substitution, and without departure from the spirit and scope of technical solution of the present invention, it all should cover in the present invention
Right among.
Claims (6)
- A kind of 1. two-phase compositions of lead accumulator, it is characterised in that described two-phase compositions are based on 100 parts by volume, by The silicone composition of 10~90 parts by volume and the silica mixed liquor of 10~90 parts by volume combine；Described siloxanes Composition is based on 100 parts by volume, including following components and content：Component A：Main chain backbone is (- Si-O-Si-) structure and side base contains more than one unsaturated hydrophilic active group R, molecular weight Siloxanes less than 3000,2~15 parts by volume；B component：Viscosity is less than the organic silicon rubber of 1500 pas, 2~15 parts by volume；Component C：10wt%-30wt% methyl silicate, 68~95.8 parts by volume；D components：The water miscible parts by volume of polyvinyl alcohol 0.2~1, described water miscible polyvinyl alcohol be active matter content 8~ 10% fluid product；Described silica mixed liquor is based on 100 parts by volume, including following components and content：Aerosil：5~15 parts by volume；Industrial pure water：83~94.8 parts by volume；Lauryl sodium sulfate：0.2~2 parts by volume, described lauryl sodium sulfate are the liquid of active matter content 30~40% Body product.
- 2. the two-phase compositions of lead accumulator according to claim 1, it is characterised in that the component A siloxanes side base Contained R includes H, OH, SO2H、NH2、CH3Or other unsaturated hydrophilic active groups.
- 3. the two-phase compositions of lead accumulator according to claim 1, it is characterised in that the organosilicon rubber of the B component Glue includes methyl silicone rubber, ethyl silicon rubber, methyl phenyl silicone rubber, the organosilicon containing nitrile silicone rubber or containing other organic groups Rubber.
- 4. the two-phase compositions of lead accumulator according to claim 1, it is characterised in that the component of the two-phase compositions It is additionally included in the alkaline regulator that preparation process is used for regulation composition intermediate pH value.
- 5. a kind of preparation method of the two-phase compositions based on any lead accumulator of Claims 1 to 4, including：1) described component A and described B component are thoroughly mixed and uniformly, then add described component C, be sufficiently stirred It is well mixed；2) mixture obtained to step 1) adds described D components, is thoroughly mixed and uniformly, obtains described siloxanes group Compound；3) described aerosil and described industrial pure water are uniformly mixed, used during being thoroughly mixed Described alkaline regulator adjusts the pH value of mixture to 8-10；4) mixture obtained to step 3) adds described lauryl sodium sulfate, is thoroughly mixed uniformly, obtains described Silica mixed liquor；5) by the silica mixed liquor that step 4) obtains and the silicone composition that step 2) obtains by the volume proportion model Enclose well mixed, that is, obtain two-phase compositions of the present invention.
- 6. the electrolyte of the two-phase compositions containing any lead accumulator of Claims 1 to 4 repairs liquid.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111668557A (en) * | 2020-04-29 | 2020-09-15 | 广东英业达电子有限公司 | Colloid electrolyte of nano colloid long-life battery and preparation method thereof |
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| CN1374347A (en) * | 2001-03-13 | 2002-10-16 | 刘粤荣 | Organic polymer composition for lead accumulator and its prepn and use |
| CN1383225A (en) * | 2001-04-23 | 2002-12-04 | 刘粤荣 | Electrolyte or chemical liquid composition for lead-acid accumulator and its preparing process |
| CN104091968A (en) * | 2014-07-31 | 2014-10-08 | 浙江天能电池江苏新能源有限公司 | Gel electrolyte capable of prolonging service life of lead-acid battery |
| CN104538679A (en) * | 2015-01-14 | 2015-04-22 | 山东大学 | Application of organosilicon compound serving as additive in colloid storage battery |
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2017
- 2017-09-18 CN CN201710841762.8A patent/CN107565175A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1374347A (en) * | 2001-03-13 | 2002-10-16 | 刘粤荣 | Organic polymer composition for lead accumulator and its prepn and use |
| CN1383225A (en) * | 2001-04-23 | 2002-12-04 | 刘粤荣 | Electrolyte or chemical liquid composition for lead-acid accumulator and its preparing process |
| CN104091968A (en) * | 2014-07-31 | 2014-10-08 | 浙江天能电池江苏新能源有限公司 | Gel electrolyte capable of prolonging service life of lead-acid battery |
| CN104538679A (en) * | 2015-01-14 | 2015-04-22 | 山东大学 | Application of organosilicon compound serving as additive in colloid storage battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111668557A (en) * | 2020-04-29 | 2020-09-15 | 广东英业达电子有限公司 | Colloid electrolyte of nano colloid long-life battery and preparation method thereof |
| CN111668557B (en) * | 2020-04-29 | 2022-03-18 | 广东英业达电子有限公司 | Colloid electrolyte of nano colloid long-life battery |
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Application publication date: 20180109 |