CN107611494A - A kind of two-phase for lead accumulator mixes polymers additive and preparation method thereof - Google Patents
A kind of two-phase for lead accumulator mixes polymers additive and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of two-phase for lead accumulator to mix polymers additive and preparation method thereof, and described two-phase mixes polymers additive and is based on 100 parts by volume, and component and content include：Main chain backbone is the parts by volume of organosiloxane 1~7 of (C Si O) structure and side base containing more than one unsaturated hydrophilic active groups；The parts by volume of organic silicon rubber 1~7；The parts by volume of tetraethyl orthosilicate 5~80；The parts by volume of industrial pure water 10~90；The parts by volume of aerosil 2~15；The parts by volume of lauryl sodium sulfate 0.2~1；Described two-phase is mixed polymers additive and 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, help softening positive active material to harden again, there is few, the cost-effective advantage of addition.
Description
Technical field
The present invention relates to the field of material technology of lead accumulator, a kind of more particularly to two-phase for lead accumulator mixes polymers
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 polyorganoelementosiloxane, silicone oil and positive esters of silicon acis water
The silicon composition of solution mixing, said composition and sulfuric acid liquid mixed poly- electrolyte or forming liquid as lead accumulator.Pass through
Ten several years were applied, and industry generally believes that aerosil colloid and organic polymer colloid are each has something to recommend him, the former viscosity it is high but
Life time decay is more steady, and the latter's viscosity is low and lead accumulator can obtain the income for reducing internal resistance, increasing capacity, but stability is not so good as
The former.
It is always the technology that lead accumulator industry is sought by silicon dioxide colloid and the mutual supplement with each other's advantages of silicon composition colloid
Scheme, but some two class finished product colloids are simply mixed the method that uses and unsatisfactory, and technical reason is：Some finished product colloids
For good dispersion, the emulsifying agent for having used some to belong to impurity to lead accumulator, this kind of emulsifying agent such as tween, Span series
Deng compound, though this kind of emulsifying agent adds silicon dioxide colloid and obtains fine dispersion system stabilization, impurity is belonged to lead accumulator,
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
Deng.Therefore, industry is wished to seek to one kind aerosil and silicon composition being fully coupled and can lift lead electric power storage
The two phase additive of pond performance.
The content of the invention
It is an object of the invention to：For current lead accumulator in the market silicon dioxide colloid and silicon composition colloid
Technological deficiency, there is provided one kind not only can fully be coupled aerosil and silicon composition but also in the two-phase mixes polymers
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 technical goal to increase the service life.
To achieve the above object, the invention provides a kind of two-phase for lead accumulator to mix polymers additive, described
Two-phase mixes polymers additive and is based on 100 parts by volume, including following components and content：
Component A：Main chain backbone is (- C-Si-O-) structure and side base contains more than one unsaturated hydrophilic active group R, divided
Organosiloxane of the son amount less than 3000,1~7 parts by volume；
B component：Viscosity is less than the organic silicon rubber of 1500 pas, 1~7 parts by volume；
Component C：10wt%-35wt% tetraethyl orthosilicate, 5~80 parts by volume；
Industrial pure water：Industrial pure water, 10~90 parts by volume；
Aerosil：2~15 parts by volume；
The parts by volume of lauryl sodium sulfate 0.2~1, 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.
The above-mentioned two-phase for lead accumulator is mixed in the component of polymers additive, the component A organosiloxane side base institute
The R contained includes H, OH, SO2H、NH2、CH3Or other unsaturated hydrophilic active groups.
The above-mentioned two-phase for lead accumulator is mixed in the component of polymers additive, and the organic silicon rubber of the B component includes
Methyl silicone rubber, ethyl silicon rubber, methyl phenyl silicone rubber or the organic silicon rubber containing other organic groups.
The above-mentioned two-phase for lead accumulator is mixed in the component of polymers additive, and it is mixed for adjusting to be additionally included in preparation process
The alkaline regulator of polymers intermediate pH value.Described described alkaline regulator includes but is not limited to using sodium hydroxide, hydrogen
Potassium oxide.
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 two-phase in pond mixes the preparation method of polymers additive, and this 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) another described lauryl sodium sulfate is well mixed with described industrial pure water, then adds described gas
Aerosil, it is thoroughly mixed uniformly；
5) described alkaline regulator is used to adjust the pH value of mixture obtained by step 4) to 8-10 in being stirred；
6) mixture that step 5) obtains is well mixed with the mixture that step 3) obtains in being sufficiently stirred, that is, obtained
Two-phase of the present invention mixes polymers additive.
Present invention also offers a kind of electrolyte containing the mixed polymers additive of the above-mentioned two-phase for lead accumulator or repair
Multiple liquid.The sulfuric acid liquid of the electrolyte or reparation liquid using density as 1.05-1.35 is key component, described to be used for lead accumulator two
Mutually mixed polymers additive is not less than 0.2% in the volume content of the electrolyte, is not less than in the volume content of the reparation liquid
2%.
In the present invention, the viscosity for the mixed polymers additive of two-phase produced with the material prescription and preparation technology is low, adds
Gel is slow after adding sulfuric acid liquid, is typically added into the technological requirement that sulfuric acid liquid a few hours still meet conventional 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 silicon 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, gel
Overrun, filling process it is poor, it is low that the lead accumulator of supporting making shows as initial capacity；And if silicon composition can not be made
It is made particle diameter and is less than 10 nanometers of ball shape structure, the organic colloid viscosity that sulfuric acid liquid is produced is small, gel is slow, fills although being added into
Good manufacturability is filled, 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 mixed poly- two-phases used are mixed into polymers additive can preferably overcome silicon dioxide colloid and siloxanes group
The shortcomings that compound colloid.
The present invention mixes the adjustment effect of polymers additive preparation process by lauryl sodium sulfate component in two-phase, effectively
Ground improves the electro-chemical activity that the two-phase mixes polymers additive.As it was previously stated, some aerosil colloids in order to point
It is good to dissipate property, the emulsifying agent such as tween, Span series has been 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 silicon composition, so as to avoid
Using the impurity emulsifying agent of the electro-chemical reactions such as tween, Span series, the electrochemistry work that two-phase of the present invention mixes polymers additive is lifted
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 is mixed polymers and added
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 for lead accumulator of the present invention is mixed polymers additive and preparation method thereof advantage and 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 mixes what is gathered in organic phase and inorganic phase
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, using effect is good, and purposes is wide.
Embodiment
Polymers additive further is mixed to a kind of two-phase for lead accumulator of the present invention with reference to embodiment
Material, formula and its and its prepare process be described in detail.
Component A organosiloxane of the present invention is a species in organosilicon material, and its architectural feature is main chain
Skeleton has m (- C-Si-O-) segments, the positive integer of described m Wei≤1, and its side base (side chain) has more than one unsaturation
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 organosiloxane of (- C-Si-O-) segmented structure, all side bases (side chain) are contained
The poly- element siloxanes of unsaturated hydrophilic active group can select with B component organic silicon rubber be coupled, for ensure component A and
B component is easier to be coupled under normal conditions, and is easily diluted after being copolymerized with B component, the A that molecular weight should be selected to be less than 3000
Component.
Another species in the organic silicon rubber category organosilicon material of the B component, its product line include methyl silicon
Rubber, ethyl silicon rubber, methyl phenyl silicone rubber or the organic silicon rubber containing other active groups, there is the chain of different polymerization degree
Structure, with chain hop count n increases, molecular weight increases, and viscosity increases, and viscosity should be selected during application to be less than the organosilicon of 1500 pas
Rubber product, such flowable organic silicon rubber are commonly called as liquid silastic；One of important function of B component, it is as component A
Molecular structure segment end-capping reagent.
Described component C is the 10wt%-35wt% tetraethyl orthosilicate aqueous solution, and the chemical formula of tetraethyl orthosilicate is Si
(OC2H5)4, be good organic solvent and organic synthesis intermediate, there is both sexes coupling, the important function of component C it
One, 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 and A
When component and B component are copolymerized, the scattered silicon composition system evenly of differential is easily formed；A kind of two-phase interface theory is recognized
For 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
Formed and be more beneficial for the passage that ion cluster gathering closes directed movement, the ability of increase ion set transition in the channel, meanwhile, this
One combined electrolysis plastidome be advantageous to middle electrode and electrolyte two-phase interface formed dynamic equilibrium absorption electric double layer, strengthen from
The activation energy that son reacts in electrode surface, accelerates 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 that the two-phase mixes polymers additive；Industrial pure water is routinely to pass through 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 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,
The dispersion effect meeting that industrial pure water is added after hydrophilic based surfactants to aerosil is more preferable.
Described alkaline regulator is used for the pH value for adjusting preparation process intermediate, and its selection includes all achievable centres
Body pH value adjusts and will not produce the basic species of sediment, and alkaline regulator belongs to micro in the two-phase mixes polymers additive,
Material selection is wide, but considers preferred sodium hydroxide or potassium hydroxide from cost performance.In the mixed polymers addictive preparation method
The main function of the intermediate pH value is adjusted, is that can make aerosil in lauryl sodium sulfate water in alkaline environment
The fine dispersion system formed in solution is more stable, so as in the more stable fine dispersion of the mixed poly- middle formation of further two-phase thing
System.
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 that the two-phase mixes the synthetic effect of polymers additive, and the two-phase of contaminant overstandard is mixed poly-
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 that the two-phase mixes polymers additive.
Two-phase of the present invention for lead accumulator, which mixes polymers additive, to use one kettle way to mix, and 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) another described lauryl sodium sulfate is well mixed with described industrial pure water, then adds described gas
Aerosil, it is thoroughly mixed uniformly；
5) described alkaline regulator is used to adjust the pH value of mixture obtained by step 4) to 8-10 in being stirred；
6) mixture that step 5) obtains is well mixed with the mixture that step 3) obtains in being sufficiently stirred, that is, obtained
Two-phase of the present invention mixes polymers additive.
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 silicon composition 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 6) with the gas phase two of aqueous phase
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.Industrial pure water addition lauryl sodium sulfate can be made into aerosil in water
Degree of scatter in solution is more preferable.When obtained mixture clarity deficiency (big generally with apparent viscosity), can also pass through
The material ratio for adjusting the industrial pure water containing lauryl sodium sulfate and aerosil carrys out regulating step 4) gained mixture
Clarity.
Above-mentioned steps 5) in the pH value of step 4) mixture is adjusted to 8-10, be in order that step 4) formed mixture
It is more stable in the basic conditions, so as to which the mixture obtained in step 6) with step 3) forms stable fine dispersion system.
In step 6), recommend mixture obtained by step 3) being slowly injected into the mixture that step 5) obtains, and hold in being slowly injected into
It is continuous to stir.In order that the quality that two-phase mixes polymers additive is more preferable, conventional filtration technique can be increased afterwards in step 6).Institute
State the mixed polymers additive of two-phase to complete after preparing, if desired for long-term storage, can continue to add alkaline regulator in right amount by its PH
Value regulation is 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.
It is a kind of typical micro- dispersoid that two-phase of the present invention for lead accumulator, which mixes polymers additive, 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 that two-phase mixes polymers additive is obvious, illustrates that making reaches Technology design target；Conversely, it can verify made
Two-phase to mix polymers additive system unsuccessful.
More deep personnel are studied for this area, above-mentioned preparation method can equally be replaced by adjusting mixed process
Change, such as first operating procedure 4) and step 5) operating procedure 2 afterwards) and a kind of step 3) sheerly displacement of intermediate stock；Make
The change of intermediate process condition easily produces isomers, can influence two-phase and mix the electrochemistry that polymers additive is added after sulfuric acid liquid
Effect.Different selections and the married operation that feeds intake, on the premise of final mixture is similar, it is possible that clarity and electrification
The contradiction of effect is learned, the latter is 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 the mixed polymers additive of this two-phase is mixed with other conventional additives, it is necessary first to pay attention to mixed with other additives
When whether occur precipitating or viscosity increases to and is difficult to be filled into inside lead accumulator, simultaneously, it is necessary to using other additives with
Performance of lead-acid battery is completely examined, to determine the mixtures' ratio with other additives.
The electrolyte of polymers additive preparation lead accumulator sulfuric acid liquid is mixed with two-phase of the present invention, filling lead stores
Battery has the obvious technical advantage of following items：
1st, the coupling of inorganic aerosil and silicon composition is stable, is added into the sulfuric acid liquid tool of lead accumulator
The double technique advantage of standby aerosil colloid and silicon composition colloid；
2nd, after the mixed poly- 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 it is a kind of add it is mixed poly- in lead accumulator sulfuric acid liquid, the two-phase that can increase the anti-softening ability of positive active material
Thing additive, stocks up first, and the two-phase mixes polymers additive in terms of 100 parts by volume, and component and content are：
Component A：There is the organosiloxane of some (- C-Si-O-) segmented structures using a kind of main chain backbone, its side base contains
H, molecular weight 1200, addition are 7 parts by volume；
B component：Viscosity be 1000 pas methyl silicone rubber, 7 parts by volume；
Component C：15wt% tetraethyl orthosilicate, 56 parts by volume；
Industrial pure water：27.5 parts by volume；
Aerosil：2 parts by volume (scaled value of weight/proportion)；
Active matter content is 40% lauryl sodium sulfate fluid product：0.5 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 7 parts by volume and the B component of 7 parts by volume are thoroughly mixed uniformly, then add 56 parts by volume
Component C, it is thoroughly mixed uniformly；
3) HLB of mixture obtained by step 2) is adjusted to 12 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 12, 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 4), otherwise, is needed
Increase the content of the lauryl sodium sulfate；
4) another described lauryl sodium sulfate is well mixed with the industrial pure water of 27.5 parts by volume, then adds 2
The aerosil of parts by volume, stir 5 minutes；
5) use described sodium hydroxide to adjust the pH value of mixture obtained by step 4) to 8 in being stirred, persistently stir
Mix 20 minutes；
6) mixture for obtaining step 3) is slowly injected into the mixture that step 5) obtains, and is fully stirred in injection process
Mix well mixed, gained mixture is that two-phase of the present invention mixes polymers additive.
Above-mentioned preparation method is stirred at normal temperatures and pressures, and the two-phase of gained mixes polymers additive need to such as deposit for a long time,
Sodium hydroxide can be added in right amount to adjust its pH value to 11.The two-phase that the present embodiment obtains, which mixes polymers additive, can be used as a kind of lead
The wide spectrum additive of battery sulfuric acid liquid, different proportion is added according to different purposes.
Embodiment 2
The two-phase of the gained of embodiment 1 is mixed into the sulfuric acid liquid of polymers additive and density 1.245 by volume 1：99 mixing are equal
It is even, turn into a kind of two-phase and mix polymers additive and the mixed poly- colloidal electrolyte of 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 an extraordinary colloid plumbic storage battery of resistant to elevated temperatures outdoor energy storage.The two-phase of the present embodiment
Mixed polymers additive is with volume ratio 1：The filling lead accumulator of 99 mix sulphur acid solutions uses, can under the liquid-tight degree same case of sulfuric acid
Lead accumulator is set substantially to obtain the effect for reducing internal resistance.
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 0.5% of the colloidal electrolyte volume total amount, and industry is generally accepted, and adds in colloidal electrolyte and necessarily contains
The anhydrous sodium sulfate of amount, electrolyte electrochemical activity can be lifted, reduces the internal resistance of colloid plumbic storage battery, lifts leaching colloidal electric power storage
The charge acceptance in pond.
Embodiment 3
In embodiment 1, aerosil is 2 parts by volume in the content that the two-phase mixes polymers additive, this implementation
Aerosil increase is 6 parts by volume by example, i.e., the total amount of the mixed polymers additive of two-phase is 104 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：Silicon composition is different from the proportioning of aerosil, and two
Mutually mixed polymers additive can show different electrochemical properties, when two-phase mixes polymers additive based on silicon 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 of the present embodiment mixes polymers additive 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
Design a kind of electrolysis additive for adapting to the lead accumulator that long-term floating charge system uses, its organic polymer composition
Component and content in terms of 100 parts by volume：
Component A：Used organosiloxane is that main chain backbone has some (- C-Si-O-) 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 rubber, 1 parts by volume；
Component C：35wt% tetraethyl orthosilicate, 8 parts by volume；
Industrial pure water：74 parts by volume；
Aerosil：15 parts by volume；
Active matter content is 30% lauryl sodium sulfate fluid product：1 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 8 parts by volume
Component, it is thoroughly mixed uniformly；
3) HLB of mixture obtained by step 2) is adjusted to 13 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 13, 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 4), otherwise, is needed
Increase the content of the lauryl sodium sulfate.
4) another described lauryl sodium sulfate is well mixed with the industrial pure water of 74 parts by volume, then adds 15 bodies
The aerosil of product part, the process for mixing aerosil are pressurizeed and heated using reactor and help reaction, and 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 20 minutes；If mixture
Clarity deficiency or viscosity are bigger than normal, can pass through industrial pure water of the adjustment containing lauryl sodium sulfate and the ratio of aerosil
Example adjusts the clarity of this step mixture.
5) to the potassium hydroxide described in the mixture obtained by step 4) in right amount addition, by obtained by step 4) in being stirred
The pH value of mixture is adjusted to 10, is persistently stirred 5 minutes；
6) mixture for obtaining step 3) is slowly injected into the mixture that step 5) obtains, and is sufficiently stirred in injection process
It is well mixed, gained mixture is filtered, filtrate is that described two-phase mixes polymers additive.
Content of the present embodiment because of aerosil in two-phase mixes polymers additive is higher, with suitable system after sulfuric acid liquid
Make Large Copacity lead accumulator, be especially suitable for the Large Copacity energy storage lead accumulator for making long-term floating charge.
Embodiment 5
The two-phase that embodiment 1 is obtained mixes polymers additive and 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 mixes the homogenized deep processing processing of polymers additive, and close
Spend the lead accumulator sulfuric acid liquid by volume 1 for 1.20：10 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 by 1.1ml/10Ah quantify be added into through being judged as positive material(PAM) softening and
Inside the lead accumulator of capacity attenuation, the inner panel group through adding negative pressure technique to make the reparation liquid in lead accumulator known to industry
After being evenly distributed, by secondary formation charging technique known to industry, the positive plate active material of softening is hardened again, make this
The positive plate active material of lead accumulator to be repaired 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 for lead accumulator mixes polymers additive, it is characterised in that is mixed based on the two-phase described in 100 parts by volume
Polymers additive, including following components and content：
Component A：Main chain backbone is (- C-Si-O-) structure and side base contains more than one unsaturated hydrophilic active group R, molecular weight
Organosiloxane less than 3000,1~7 parts by volume；
B component：Viscosity is less than the organic silicon rubber of 1500 pas, 1~7 parts by volume；
Component C：10wt%-35wt% tetraethyl orthosilicate, 5~80 parts by volume；
Industrial pure water：10~90 parts by volume；
Aerosil：2~15 parts by volume；
The parts by volume of lauryl sodium sulfate 0.2~1, described lauryl sodium sulfate are the liquid of active matter content 30~40%
Product.
2. the two-phase for lead accumulator mixes polymers additive according to claim 1, it is characterised in that the component A has
R contained by organic siloxane side base includes H, OH, SO2H、NH2、CH3Or other unsaturated hydrophilic active groups.
3. the two-phase for lead accumulator mixes polymers additive according to claim 1, it is characterised in that the B component
Organic silicon rubber includes methyl silicone rubber, ethyl silicon rubber, methyl phenyl silicone rubber or the organosilicon rubber containing other organic groups
Glue.
4. the two-phase for lead accumulator mixes polymers additive according to claim 1, it is characterised in that the two-phase is mixed poly-
The component of thing additive is additionally included in the alkaline regulator that preparation process is used to adjust mixed polymers intermediate pH value.
5. a kind of preparation method that polymers additive is mixed based on any two-phase 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) another described lauryl sodium sulfate is well mixed with described industrial pure water, then adds described gas phase two
Silica, it is thoroughly mixed uniformly；
5) described alkaline regulator is used to adjust the pH value of mixture obtained by step 4) to 8-10 in being stirred；
6) mixture that step 5) obtains is well mixed with the mixture that step 3) obtains in being sufficiently stirred, that is, obtains this hair
Bright described two-phase mixes polymers additive.
6. mix the lead storage battery electrolytic solution of polymers additive containing any two-phase of Claims 1 to 4 or repair liquid.
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Cited By (1)
| 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 |
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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 CN201710840303.8A patent/CN107611494A/en not_active Withdrawn
Patent Citations (4)
| 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: 20180119 |