CN107579289A - A kind of two-phase polymer additive for lead accumulator and preparation method thereof - Google Patents
A kind of two-phase polymer additive for lead accumulator and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of two-phase polymer additive for lead accumulator and preparation method thereof, described two-phase polymer additive is based on 100 parts by volume, and component and content include：Main chain backbone is the parts by volume of siloxanes 1~6 of (Si O Si) structure and side base containing more than one unsaturated hydrophilic active groups；The parts by volume of organic silicone oil 1~6；The parts by volume of methyl silicate 5~80；The parts by volume of industrial pure water 10~88；The parts by volume of aerosil 3~15；The parts by volume of lauryl sodium sulfate 0.2~2；Described two-phase polymer additive is prepared by process of the present invention, it mixes conventional sulfuric acid liquid and added inside lead accumulator, the anti-softening ability of positive active material can be strengthened, there is the effect of helping softening positive active material to harden again, addition is few, cost-effective.
Description
Technical field
The present invention relates to the field of material technology of lead accumulator, more particularly to a kind of two-phase polymer for lead accumulator
The material of additive, formula and preparation method thereof.
Background technology
In recent years the battery of energy storage market common requirements Large Copacity is made with applying mechanically, but conventional battery table in use 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
Appropriate colloidal substance is added in liquid, can effectively lift the life-span used out of doors.Lead storage battery electrolytic solution tradition uses
Colloid is aerosil, aerosil is fully liquefied by industrial pure water or other solvent methods during use；
In Chinese invention patent publication number CN1383225A, one kind is disclosed by poly- element siloxanes, silicone oil and positive silicic acid aqueous solution of ester
The silicone composition of mixing, said composition polymerize electrolyte or forming liquid as lead accumulator with sulfuric acid liquid.Pass through ten numbers
Year application, industry generally believe that aerosil colloid and high molecular weight siloxane aggregation colloid are each has something to recommend him, and the former viscosity is high
But life time decay is more steady, the latter's viscosity is low and lead accumulator can obtain the income for reducing internal resistance, increasing capacity, but stability is not
Such as the former.
It is always what lead accumulator industry was sought that aerosil colloid and silicone composition colloid, which are had complementary advantages,
Technical scheme, but some two class finished product colloids are simply mixed the method used is unsatisfactory, and technical reason is：Some finished product glue
Body is for good dispersion, the emulsifying agent for having used some to belong to impurity to lead storage battery electrolytic solution, this kind of emulsifying agent such as tween,
The compounds such as Span series, though this kind of emulsifying agent adds silicon dioxide colloid and obtains fine dispersion system stabilization, to lead accumulator
Belong to impurity, it is not good enough that it is added into the performance of the lead accumulator electrochemistry after sulfuric acid liquid, such as reduces electro-chemical activity, weakens low temperature
Charging ability etc..Therefore, industry wishes to seek fully to be coupled aerosil with silicone composition to one kind and can carry
Rise the two phase additive of performance of lead-acid battery.
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 polymer
The additive of the conventional electrolyte activating agent of implantation, 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 technology application target to increase the service life.
To achieve the above object, it is described the invention provides a kind of two-phase polymer additive for lead accumulator
Two-phase polymer additive 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, divided
Siloxanes of the son amount less than 3000,1~6 parts by volume；
B component：Viscosity is less than the organic silicone oil of 2000 pas, 1~6 parts by volume；
Component C：10wt%-30wt% methyl silicate, 5~80 parts by volume；
Industrial pure water：10~88 parts by volume；
Aerosil：3~15 parts by volume；
The parts by volume of lauryl sodium sulfate 0.2~2, described lauryl sodium sulfate are active matter content 30~50%
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 above-mentioned two-phase polymer additive, the R contained by the component A siloxanes side base includes H, OH, SO2H、
NH2、CH3Or other unsaturated hydrophilic active groups.
In the component of above-mentioned two-phase polymer additive, the B component organic silicone oil include methyl-silicone oil, ethyl silicon oil,
Phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid or the organic silicone oil containing other organic groups.
In the component of above-mentioned two-phase polymer additive, it is additionally included in preparation process and is used to adjust intermediate polymer pH value
Alkaline regulator.Described alkaline regulator includes but is not limited to using sodium hydroxide, potassium hydroxide.
Based on above-mentioned material and ratio range, the stock is fabricated to for lead electric power storage present invention also offers one kind
The preparation method of the two-phase polymer additive in pond, this method include：
1) described lauryl sodium sulfate is divided into two parts, it is standby by application target；
2) described component A and described B component are thoroughly mixed and uniformly, then add described component C, fully
It is uniformly mixed；
3) HLB of mixture obtained by step 2) is adjusted to 10~14 with a copy of it lauryl sodium sulfate；
4) described industrial pure water is well mixed with described aerosil, and institute is used in being thoroughly mixed
The alkaline regulator stated adjusts the pH value of mixture to 8-10；
5) another described lauryl sodium sulfate is added into the mixture that step 4) obtains, be uniformly mixed；
6) mixture that step 3) obtains is well mixed with the mixture that step 5) obtains in being sufficiently stirred, that is, obtained
Two-phase polymer additive of the present invention.
Present invention also offers a kind of lead storage battery electrolytic solution containing above-mentioned two-phase polymer additive or repair liquid.Institute
It is 1.05-1.35 sulfuric acid liquid for key component to state electrolyte or repair liquid using density, and the two-phase polymer additive is in institute
The volume content for stating electrolyte is not less than 0.2%, is not less than 2% in the volume content of the reparation liquid.
In the present invention, the viscosity for the two-phase polymer additive produced with the material prescription and preparation technology is low, adds
Gel is slow after adding sulfuric acid liquid, is typically added into sulfuric acid liquid a few hours and still meets technological requirement to lead accumulator routine liquid filling,
And versatility is good, can be used in mixed way with other conventional additives of lead storage battery electrolytic solution.
Aerosil colloid and silicone composition colloid have respective advantage and disadvantage, industrial gas aerosil
Spatial volume belong to non-type structure, when its average grain diameter is more than tens nanometer, produced inorganic colloid viscosity is big,
Gel is overrun, filling process is poor, and it is low that the lead accumulator of supporting making shows as initial capacity；And aforementioned silicone composition is such as
Fruit can not be fabricated to particle diameter and be less than 10 nanometers of ball shape structure, although be added into the organic colloid viscosity that sulfuric acid liquid is produced it is small,
Gel is slow, 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.Both are polymerize the two-phase polymer additive used can preferably overcome silicon dioxide colloid and
The shortcomings that silicone composition colloid.
The present invention by lauryl sodium sulfate component in the adjustment effect of two-phase polymer additive preparation process, have
Improve to effect the electro-chemical activity of the two-phase polymer additive.As it was previously stated, some aerosil colloids in order to
Good dispersion, the emulsifying agent such as tween, Span series is used in water dispersion solution, miscellaneous is belonged to lead storage battery electrolytic solution
Matter, the electro-chemical activity of lead accumulator can be reduced, weaken low temperature charging ability etc., the present invention adds in the aerosil aqueous solution
The lauryl sodium sulfate entered is a kind of good electrolyte activating agent, and its hydrophilic lipophilic balance (HLB) is 40, is had good
The hydrophilic group surface-active of dispersive property, can promote the coupling of aqueous silica solution and silicone composition, so as to avoid
Using the impurity emulsifying agent of the electro-chemical reactions such as tween, Span series, the electrochemistry for lifting two-phase polymer additive of the present invention is lived
Property and low temperature charging ability.
The described additive, which adds sulfuric acid liquid, has percdation ability to chloride plate, can slow down positive-active
Material lattice avalanche speed caused by lead sulfate oxidationreduction, make cycle life must give extension (lead accumulator end-of-life
Main cause is caused by positive material(PAM) softening, accounts for end-of-life probability 80%), now described two-phase polymer adds
Agent is added to can be considered a kind of reinforcing agent used for positive pole.Similarly, to confirming that the capacity attenuation lead of positive material(PAM) softening stores
Battery, the additive add sulfuric acid liquid and can be considered a kind of reparation liquid.
A kind of two-phase polymer additive for lead accumulator of the present invention and preparation method thereof advantage is：
The two-phase mixtures additive produced with material prescription of the present invention and preparation method, can add by a certain percentage
Add sulfuric acid liquid and make electrolyte, the lauryl sodium sulfate of two-phase mixtures additive implantation is in organic phase and inorganic phase-polymerization
Fine dispersion system helps to lift the electro-chemical activity of lead accumulator, is a kind of to have the two of good effects to positive active material
Phase colloidal additive, purposes is wide, and using effect is good.
Embodiment
With reference to embodiment further to a kind of two-phase polymer additive for lead accumulator of the present invention
Material, formula and its and its prepare process be described in detail.
Component A siloxanes of the present invention is one kind in silicon-containing polymer, and its architectural feature is main chain bone
Frame has m (- Si-O-Si-) segments, the positive integer of described m Wei≤1, and its side base (side chain) contains more than one insatiable hunger
With hydrophilic active group R, wherein described R includes but is not limited to H, OH, SO2H、NH2、CH3Deng or other are unsaturated
Hydrophilic active group；In numerous main chain backbones in the siloxanes of (- Si-O-Si-) segmented structure, all side bases (side chain) are not containing
The poly- element siloxanes of saturation hydrophilic active group can select to be coupled with B component organic silicone oil, 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 silicone oil category organosilicon material of the B component, also known as silicone grease, silicon emulsion, silicon dodecane
Base sodium sulphate etc., described organic silicone oil include methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, aminomethyl phenyl
Silicone oil, cyanoethyl methyl polysiloxane or the organic silicone oil containing other organic groups, there is the chain structure of different polymerization degree, as chain hop count n increases
Add and molecular weight increases, viscosity increases, and viscosity should be selected during application to be less than the organic silicone oil product of 2000 pas；B component it is important
One of effect, 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, it is easier to form uniform fine dispersion system；A kind of two-phase interface theory thinks, (A+B+C)
Copolymer mixture can form special compound bone, can make (A+B+C) be copolymerized after segmented structure in electrolyte system shape
Into the passage for being more beneficial for ion cluster gathering and closing 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 ion
In the activation energy of electrode surface reaction, accelerate the reaction speed of electrode, so as to strengthen the high current respond of electrode.
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 polymer additive；Industrial pure water is routinely to pass through source water
Electric dialyzator 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 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 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, general all higher, the active matter content one of fluid product of active matter content in procurement of commodities
As all >=27%, should be diluted through industrial pure water or other solvents during as dispersant.Lauryl sodium sulfate is in the present invention
Main function has three, first, the excellent activity agent of lead storage battery electrolytic solution；Second, in preparation process adjusts (A+B+C) copolymer
The HLB of mesosome, the experiences that are about worth of HLB are estimated according to water-soluble method, the HLB of (A+B+C) copolymer being typically prepared 7~
9, when polymerizeing with aqueous-phase material, the effect for its HLB being adjusted to 10~14 adaptation values can be more preferable；Third, according to operating experience,
Hydrophilic based surfactants are added in the aqueous solution of aerosil can obtain the more stable effect of dispersion effect.
Described alkaline regulator is used to adjusting the pH value of preparation process intermediate, its selection include it is all can be by intermediate
To realize pH value adjustment and the basic species of sediment will not be produced, alkaline regulator belongs to micro in the two-phase mixtures additive,
Material selection is wide, but the preferred sodium hydroxide of cost performance or potassium hydroxide.Adjusted in the polymeric additive preparation method
The main function of intermediate pH value, it is that in alkaline environment the dispersiveness of the aerosil aqueous solution can be made more preferable, so as to enter
More stable fine dispersion system is formed in the two-phase thing polymerization of one step.
Above-described raw material can be purchased commercially, and the purity requirement of the aerosil reaches
99.99%, the purity requirement of the component A, B component, component C and lauryl sodium sulfate is at least technical pure, and SILVER REAGENT is more
Good, raw material contaminant overstandard influences whether the synthetic effect of the two-phase polymer additive, by two phase-polymerizations of contaminant overstandard
Thing additive is added into the electrolyte of lead accumulator, can cause lead accumulator increase self discharge or even produce other side effects, together
When can influence the storage period of the two-phase polymer additive.
Two-phase polymer additive of the present invention for lead accumulator can not use one kettle way to mix, and be abided by after need to stocking up
Follow certain process to prepare, the preparation method includes：
1) described lauryl sodium sulfate is divided into two parts, it is standby by application target；
2) described component A and described B component are thoroughly mixed and uniformly, then add described component C, fully
It is uniformly mixed；
3) HLB of mixture obtained by step 2) is adjusted to 10~14 with a copy of it lauryl sodium sulfate；
4) described industrial pure water is well mixed with described aerosil, and institute is used in being thoroughly mixed
The alkaline regulator stated adjusts the pH value of mixture to 8-10；
5) another described lauryl sodium sulfate is added into the mixture that step 4) obtains, be uniformly mixed；
6) mixture that step 3) obtains is well mixed with the mixture that step 5) obtains in being sufficiently stirred, that is, obtained
Two-phase polymer additive of the present invention.
Above-mentioned steps 1) quantitative ratio for lauryl sodium sulfate being divided into two parts requires looser, also with stir it is mixed
It is related (such as the environment temperature and environmental stress being stirred) to close the operating condition of step, in general, dodecyl sulphate
As long as sodium dosage reaches HLB regulation targets and the step 4) use of the step 3).
Above-mentioned steps 2) in, the preferable silicone combinations objects system of mobility can be formed under normal condition.
Above-mentioned steps 3) HLB of mixture obtained by step 2) is adjusted, it is therefore an objective in step 5) with aqueous-phase material gas phase two
The mixed effect of aktivton is more preferable.
Above-mentioned steps 4) in practical operation, because of the more difficult accurate measuring of the actual volume of aerosil, use volume instead
It is more convenient with the parts by weight metering of proportion product.The pH value by the aerosil aqueous solution is adjusted to 8-10, be in order to
Make the aerosil aqueous solution in the basic conditions scattered more stable.As insufficient (the usual companion of obtained mixture clarity
It is big with apparent viscosity), its clarity can also be adjusted by adjusting the material ratio of industrial pure water and aerosil.On
The effect for stating step 5) is regulating step 4) gained mixture HLB, make the mixture that step 5) obtains in rapid two-phase thing 6)
It is coupled more preferably in polymerization.
Above-mentioned steps 6) in, recommend mixture obtained by step 3) being slowly injected into the mixture that step 5) obtains, and
Persistently stirred in being slowly injected into.In order that the quality of two-phase polymer additive is more preferable, can increase afterwards often in step 6)
Advise filtering technique.The two-phase polymer additive, if desired for long-term storage, can continue to add alkali in right amount after completing to prepare
Property regulator such as sodium hydroxide adjusts its pH value to more than 10.
Being stirred described in method made above can be carried out at normal temperatures and pressures, and described is stirred including rotation
Formula stirring, the shearing stirring of periodicity or corner cut at random, it can also heat, reaction is helped using compressive reaction kettle, such as mixed
The temperature that mixture is kept during being stirred of compound is 75 DEG C ± 15 DEG C；When adding reaction pressure to mix using reactor
When, kettle pressure is no more than 25MPa.
Two-phase polymer additive of the present invention for lead accumulator is a kind of typical micro- dispersoid, is made
Make success and associated with preparation method larger, its production effect can pass through the Tyndall to colloidal dispersion
(Tyndall) phenomenon is tested；Known in industry, wavelength is that 400-700mm light passes through microdispersed colloid
During system, if dispersed colloid particle diameter is less than lambda1-wavelength and can scattered, current general experiment conclusion
For：As particle diameter≤94nm of colloidal dispersion system, luminous intensity is hit in scattering and the biquadratic of wavelength is inversely proportional.Prepared
The Tyndall phenomenon of two-phase polymer additive is obvious, illustrates that making reaches Technology design target；Conversely, it can verify made
Two-phase polymer additive system it is unsuccessful.
More deep personnel are studied for this area, and above-mentioned preparation method can be carried out etc. by adjusting mixed process completely
With replacing, such as first operating procedure 4) and step 5) operating procedure 2 afterwards) and a kind of step 3) displacement that sheerly intermediate is stocked up；
The change for making intermediate process condition easily produces isomers, can influence the electricity that two-phase polymer additive is added after sulfuric acid liquid
Chemical efficiency.Different selection and the married operation that feeds intake, on the premise of final mixture is similar, it is possible that clarity with
The contradiction of 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, recommend electrochemistry
Effect preferably process for refining.
When this two-phase polymer additive is mixed with other conventional additives, it is necessary first to notice whether mixed effect occurs
Precipitation or viscosity increase to and are difficult to be filled into inside lead accumulator, simultaneously, it is necessary to the lead accumulator to using other additives with
It can be completely examined, the mixtures' ratio with other additives is determined with cost performance.
The electrolyte of lead accumulator sulfuric acid liquid is prepared with two-phase polymer additive of the present invention, filling lead stores
Battery 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 aggregation colloid 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
A kind of target is designed to add in lead accumulator sulfuric acid liquid, the two of the anti-softening ability of positive active material can be increased
Gathering compound additive, in terms of 100 parts by volume, component and content are the two-phase polymer additive：
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 6 parts by volume；
B component：Viscosity be 1000 pas methyl-silicone oil, 6 parts by volume；
Component C：20wt% methyl silicate, 58 parts by volume；
Industrial pure water：26 parts by volume；
Aerosil：3 parts by volume (scaled value of weight/proportion)；
Active matter content is 50% lauryl sodium sulfate fluid product：1 parts by volume.
In addition get the sodium hydroxide of adjustment intermediate pH value ready, prepared after completing stock with following process：
1) lauryl sodium sulfate is divided into two parts first, it is standby by application target.
2) component A of 6 parts by volume and the B component of 6 parts by volume are thoroughly mixed uniformly, then add 58 parts by volume
Component C, it is thoroughly mixed uniformly；
3) HLB of mixture obtained by step 2) is adjusted to 11 with a copy of it lauryl sodium sulfate；In this step, such as
A copy of it lauryl sodium sulfate described in fruit can not be adjusted the HLB of mixture obtained by step 2) to 11, as long as reaching step
The HLB of rapid 2) gained mixture is adjusted to more than 10, staying a lauryl sodium sulfate to be operated to step 5), otherwise, is needed
Increase the content of the lauryl sodium sulfate；
4) industrial pure water of 26 parts by volume is well mixed with the aerosil of 3 parts by volume, stirring 2 minutes, then
The pH value of mixture is adjusted to 8 with described sodium hydroxide, continues stirring 15 minutes；
5) another described lauryl sodium sulfate is added into the mixture that step 4) obtains, be uniformly mixed；
6) mixture for obtaining step 3) is slowly injected into the mixture that step 5) obtains, and is sufficiently stirred in injection process
Well mixed, gained mixture is two-phase polymer additive of the present invention.
The present embodiment preparation method is stirred at normal temperatures and pressures, and the two-phase polymer additive of gained can be used as one kind
The wide spectrum additive of lead accumulator sulfuric acid liquid, different proportion is added according to different purposes.The two-phase polymer additive of gained
Such as need to deposit for a long time, sodium hydroxide can be added in right amount and adjust its pH value to 12.
Embodiment 2
Two-phase polymer additive that embodiment 1 is obtained and density are 1.245 lead accumulator sulfuric acid liquid by volume 1：
99 is well mixed, the colloidal electrolyte polymerizeing as a kind of two-phase polymer additive with sulfuric acid liquid.
The colloidal electrolyte is filled into inside lead accumulator of the 2V500Ah energy storage with valve-regulated AGM diaphragm structures, passed through
After conventional dipping, formation charging, turn into a resistant to elevated temperatures outdoor energy storage colloid plumbic storage battery.Two phase-polymerizations of the present embodiment
Thing additive 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 0.4% of the extraordinary colloidal electrolyte volume total amount, and industry is generally accepted, and one is added in colloidal electrolyte
Determine the anhydrous sodium sulfate of content, electrolyte electrochemical activity can be lifted, reduce the internal resistance of colloid plumbic storage battery, lift leaching colloidal
The charge acceptance of battery.
Embodiment 3
In embodiment 1, aerosil is 2 parts by volume in the content of the two-phase polymer additive, this implementation
Aerosil increase is 5 parts by volume by example, i.e., the total amount of two-phase polymer additive is 103 bodies by the increase of 100 parts by volume
Product part, remaining component and content are constant, and preparation method is same as Example 1.
Typically contrast effect test result on probation is：Silicone composition is different from the proportioning of aerosil, and two
Gathering compound additive can show different electrochemical properties, when two-phase polymer additive is 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 polymer additive of the present embodiment is with volume ratio 1：The filling lead accumulator of 99 mix sulphur acid solutions uses, circulation
The life-span effect of discharge and recharge is better than embodiment 2.
Embodiment 4
Another electrolysis additive for adapting to the lead accumulator that long-term floating charge system uses is designed, its silicone composition
Component and content are in terms of 100 parts by volume：
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 1；
B component：Viscosity be 1100 pas ethyl silicon oil, 1 parts by volume；
Component C：30wt% methyl silicate, 6 parts by volume；
Industrial pure water：76.5 parts by volume；
Aerosil：15 parts by volume；
Active matter content is 30% lauryl sodium sulfate fluid product：0.5 parts by volume.
In addition get the potassium hydroxide of adjustment intermediate pH value ready, prepared after completing stock with following process：
1) lauryl sodium sulfate is divided into two parts first, it is standby by application target.
2) component A of 1 parts by volume and the B component of 1 parts by volume are thoroughly mixed the C for uniformly then adding 6 parts by volume
Component, it is thoroughly mixed uniformly；
3) HLB of mixture obtained by step 2) is adjusted to 14 with a copy of it lauryl sodium sulfate；In this step, such as
A copy of it lauryl sodium sulfate described in fruit can not be adjusted the HLB of mixture obtained by step 2) to 14, as long as reaching step
The HLB of rapid 2) gained mixture is adjusted to more than 10, staying a lauryl sodium sulfate to be operated to step 5), otherwise, is needed
Increase the content of the lauryl sodium sulfate；
4) aerosil of 15 parts by volume is well mixed with the industrial pure water of 76.5 parts by volume, mixed process uses
Reactor, which pressurizes and heated, helps reaction, and kettle pressure is 20MPa, and mixed process adds described potassium hydroxide and adjusts the pH value of mixture
Save as 10, and it is 75 DEG C ± 10 DEG C to keep the mixture temperature in kettle, is persistently stirred 25 minutes；If mixture is clear and bright
Degree deficiency or viscosity are bigger than normal, can adjust this step mixture by adjusting the ratio of industrial pure water and aerosil
Clarity.
5) another described lauryl sodium sulfate is added into the mixture that step 4) obtains, be uniformly mixed；
6) mixture obtained by step 3) is slowly injected into the mixture that step 5) obtains, be sufficiently stirred in injection process mixed
Close uniformly, gained mixture is filtered, filtrate is described two-phase polymer additive.
Content of the present embodiment because of aerosil in two-phase polymer additive is higher, with suitable system after sulfuric acid liquid
Make Large Copacity lead accumulator, be especially suitable for the outdoor energy storage lead accumulator for making long-term floating charge.
Embodiment 5
The two-phase polymer additive that embodiment 1 is obtained uses the homogenizing processing of high-speed emulsifying machine, described high speed
The homogenizing rotary speed of mulser is more than 20000 revs/min, after the two-phase polymer additive homogenized deep processing processing, and close
Spend the lead accumulator sulfuric acid liquid by volume 1 for 1.20：9 mixing are uniformly dispersed, and turn into a kind of positive electode of lead battery of repairing and live
Property material specialist 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)
1. a kind of two-phase polymer additive for lead accumulator, it is characterised in that based on two gatherings described in 100 parts by volume
Compound additive, 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 3000,1~6 parts by volume；
B component：Viscosity is less than the organic silicone oil of 2000 pas, 1~6 parts by volume；
Component C：10wt%-30wt% methyl silicate, 5~80 parts by volume；
Industrial pure water：10~88 parts by volume；
Aerosil：3~15 parts by volume；
The parts by volume of lauryl sodium sulfate 0.2~2, described lauryl sodium sulfate are the liquid of active matter content 30~50%
Product.
2. it is used for the two-phase polymer additive of lead accumulator according to claim 1, it is characterised in that the component A silicon
R contained by oxygen alkane side base includes H, OH, SO2H、NH2、CH3Or other unsaturated hydrophilic active groups.
3. it is used for the two-phase polymer additive of lead accumulator according to claim 1, it is characterised in that the B component
Organic silicone oil includes methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid or the organosilicon containing other organic groups
Oil.
4. two-phase polymer additive according to claim 1, it is characterised in that the group of the two-phase polymer additive
Divide and be additionally included in the alkaline regulator that preparation process is used to adjust intermediate polymer pH value.
5. a kind of preparation method based on any two-phase polymer additive for lead accumulator of Claims 1 to 4, bag
Include：
1) described lauryl sodium sulfate is divided into two parts, it is standby by application target；
2) described component A and described B component are thoroughly mixed and uniformly, then add described component C, be sufficiently stirred
It is well mixed；
3) HLB of mixture obtained by step 2) is adjusted to 10~14 with a copy of it lauryl sodium sulfate；
4) described industrial pure water is well mixed with described aerosil, and with described in being thoroughly mixed
Alkaline regulator adjusts the pH value of mixture to 8-10；
5) another described lauryl sodium sulfate is added into the mixture that step 4) obtains, be uniformly mixed；
6) mixture that step 3) obtains is well mixed with the mixture that step 5) obtains in being sufficiently stirred, that is, obtains this hair
Bright described two-phase polymer additive.
6. the lead storage battery electrolytic solution containing any two-phase polymer additive of Claims 1 to 4 repairs liquid.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312331A (en) * | 2001-02-23 | 2001-09-12 | 刘粤荣 | Organic high molecular composite for accumulator and its preparation method |
| 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 |
-
2017
- 2017-09-19 CN CN201710845673.0A patent/CN107579289A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312331A (en) * | 2001-02-23 | 2001-09-12 | 刘粤荣 | Organic high molecular composite for accumulator and its preparation method |
| 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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