CN104538679B - A kind of application of organo-silicon compound as additive in colloid storage battery - Google Patents
A kind of application of organo-silicon compound as additive in colloid storage battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
- H01M10/10—Immobilising of electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
A kind of application the present invention relates to organo-silicon compound as additive in colloid storage battery, the organo-silicon compound have following structure：R1‑Si(R2R3)R4, wherein, R1Si groups are HO Si groups or are various groups of the hydrolyzable into HO Si groups, R4Group is that itself can ionize out the group of Hydrogen Proton or is that can ionize out the group of Hydrogen Proton after hydrolyzing；R2、R3Group is not influence the various groups of the silicone additives self stability.The use of organo-silicon compound of the present invention, the viscosity of colloidal electrolyte can be improved, extend the encapsulating time, reduce the internal resistance of cell, obtained lead-acid accumulator low-temperature characteristics is good, self discharge is small, long lifespan, and its good heavy current, and high-multiplying power discharge capacity is big, thus it is expected to start applied to the engine of vehicle, ship and aircraft, the power supply and emergency standby power of the facility such as the electrical source of power of electric automobile and communication.
Description
Technical field
A kind of application the present invention relates to organo-silicon compound as additive in colloid storage battery, belongs to colloid electric power storage
Pond additive agent field.
Background technology
Lead-acid accumulator refer to electrode be mainly made up of lead and its oxide, electrolyte be sulfuric acid solution a kind of electric power storage
Pond, with capacity is big, uniformity and the good advantage of stability, all occupy the first place of electrochmical power source yield all the time.Leaching colloidal
Battery is one to lead-acid accumulator larger innovating reform, with convenient transportation, acid nonleakage, without acid mist, water consumption slowly, certainly
Right long lifespan, suppress pole plate corrosion and deformation, prevent active material from coming off, the advantages of maintenance period is long.Colloid plumbic storage battery is not
Only can as vehicle, ship, aircraft engine start, can also as the electrical source of power of electric automobile, communications facility power supply,
The uninterrupted power source of emergency standby power, power plant load accumulation power supply and computer in a balanced way, can also be applied to military applications,
The electronic equipment of individual soldier's carrying, the working power of navy submarine, its application field constantly expand.The rich solution grown up in recent years
The non-maintaining fixed colloid plumbic storage battery of formula, be post telecommunications system, Electric control operating system, radio system, UPS not between
The optimal power supply that power-off source etc. requires independently-powered or must not had a power failure in powering, in automotive field, fork truck field, ship domain
It is even more irreplaceable.
Gelled lead acid battery is begun one's study in 1920s by American, obtains industrialized production within 1966 years.In
State begins one's study exploitation lead-acid accumulator from the fifties, is reached a climax the beginning of the nineties at the end of the eighties.China has part producer to adopt
Colloidal electrolyte is prepared with traditional silica gel solution, the layering of colloidal electrolyte aquation, the big, short life of resistance etc. are can't resolve all the time
Shortcoming.Therefore, the colloid technology of Chinese independent research need to be broken through.
In China, electric car is a kind of important vehicles, is adapted to the level of consumption of most people, and oil price at present
Constantly soaring, environmental problem receives much concern, and this development all for the electric car of cleaning creates chance.It is general with electric car
And, electric vehicle battery also obtains huge development, and the annual production of China's electric bicycle alreadys exceed 20,000,000, it is electronic from
The annual production of driving battery is already close to 40,000,000 thousand volt-ampere hours.Battery is one of electric car core component.Lead-acid accumulator
The reliable and stable, technology maturation of energy, cheap, cost performance are higher, show one's talent from various electrochmical power sources, as electric car electricity
The main force in pond.But lead-acid battery is present that self-discharge rate is big, electrolyte stratification, sulfation, thermal runaway, deep discharge cyclicity
Can be poor the problems such as, the expectation and requirement of consumer is not reached.In order to improve battery of electric vehicle performance, it is attempted to colloid to be electrolysed
Liquid technology refers to battery of electric vehicle, but many enterprises simply add a 0.6wt% left sides in the electrolyte of battery of electric vehicle at present
Right silica, battery performance slightly has improvement, but effect is still undesirable.Obtain the electric car colloid electricity of excellent performance
Pond, it is still necessary to carry out numerous studies work.
The use of colloidal electrolyte is current mainstream development direction in analysing valve control type lead-acid accumulator battery, it can be efficiently against
The leakage of battery presence, acid solution layering, deeper cavity use not good shortcoming under discharging.Colloidal electrolyte is that influence colloid plumbic acid stores
The key factor of battery capacity and cycle life.Wherein gel, the volume fraction with glue sulfuric acid and additive etc. are all to glue
The performance of body electrolyte has an impact.
Aerosil is the electrolyte gelling agent commonly used in the world at present, uses its obtained gelled lead acid battery
Function admirable.Johnson companies of the U.S., Hagen companies of Germany and GS companies of Japan all prepare plumbic acid using aerosil
Storage-battery colloidal electrolyte.Aerosil particle surface is rich in hydroxyl, easily by hydrogen bond action in aqueous sulfuric acid
Form three-dimensional netted gel structure.Even if only preliminary gelatification, the viscosity of electrolyte also can drastically be raised, led
Cause to be difficult to pour into the battery of compact texture, the problem of encapsulating is difficult as restriction promote colloidal electrolyte application main bottleneck it
One.Found during actual silica gel storage battery production, filling colloidal electrolyte is not carried out in placement process, can be because dioxy
Reunion between SiClx colloidal solid and form precipitation, make electrolyte overall distribution uneven, in turn resulted in battery performance
Reduction.If without special viscosity modifier, deflocculant and other additives, it is difficult the property for controlling silica-gel accumulator to be
Energy and quality.
Silicon dioxide microparticle is modified with high-molecular organic material and colloidal electrolyte is made, disclosed at present
Technical literature or patent document in it has been reported that for example, Chinese patent document CN1663984A (application numbers：
200410018708.6) a kind of modified polyorganosiloxane electrolyte and preparation method thereof is disclosed, containing a variety of modified polyorganosiloxanes,
Also include tetraethyl orthosilicate, positive silicic acid propyl ester or butyl silicate；Water-soluble polypropylene acid；High-purity sulphuric acid and industrial pure water.It is poly-
Ether segment imparts colloid water solubility and hydrophily, plays emulsification, and can have good wetting action with battery lead plate.Carbon official
Carboxyl can be carried in siloxane structure, they can be formed with beneficial to H on the surface of gel particle+Conductive channel.With this kind of
Lead-acid accumulator low-temperature characteristics made from colloidal electrolyte is good, self discharge is small, long lifespan, with prominent electric recovery capability, and
And its good heavy current, the general lead-acid accumulator of high-multiplying power discharge Capacity Ratio is big by more than 30%.
But, prepare the support that thixotropy is good, the colloidal electrolyte of electrochemical performance also needs to various additives.
The viscosity of colloidal electrolyte can be improved using suitable additive, improve process for filling colloid, reduce the internal resistance of cell.Colloid electrode
Colloidal electrolyte is larger due to viscosity, and the active material above electrode is hindered during transmission, causes polar board surface
Easily form PbSO4Precipitation, reduces battery capacity, ultimate failure, and this also causes the capacity of colloid battery to be less than AGM battery.
It is unbalanced that colloid battery easily causes battery float in charging process, and colloidal electrolyte is easier in charge and discharge process
There is aquation lamination, solid-liquid occurs obvious interface, makes battery failure.Additive is added in colloidal electrolyte, is had
Have the advantages that not change that battery industry production process, fringe cost are low, effect is good, be easy to promote, all actively grind both at home and abroad at present
Miscellaneous additive agent electrolyte is made, it is to improve the main path of colloid battery performance to select suitable additive agent electrolyte.
The addition of gel additives, can change the surface state of gelinite, when gel particles are close to each other, because it is high
The steric restriction of strand, necessarily hinders interparticle further to making to be difficult to react between particle, silicon oxygen bond is difficult to shape
Into having retarding action to the colloid condensation process of gelinite.Conventional gel additives include inorganic additive, organic additive
And the species such as ionic liquid.
Conventional inorganic additive has sulfate, phosphoric acid and boric acid etc..There is document report, phosphoric acid can improve grid corrosion layer
Structure, increase active material and grid adhesion, weaving active material come off；Phosphoric acid can also reduce lead sulfate passivation layer
Formation, diffused into beneficial to acid inside pole plate and participate in reacting.Meissner thinks that phosphoric acid is added in electrolyte can influence electricity
The forming process of sulfuric acid leading crystal in pond, makes sulfuric acid leading crystal more tiny, makes the actual surface area of electrode and increases, reduction fill/
Polarization of electrode degree in discharge process, so as to reduce precipitation rate of the oxygen on electrode, reduces the fluid loss of battery, thus
The possibility that battery causes failure because of electrolyte dry-out can be reduced.Vinod thinks that the addition of appropriate phosphoric acid can increase
Positive active material and the corrosion resistance at grid alloy interface, so as to improve the deeper cavity life-span of battery.But also there is document report,
Influence of the addition of phosphoric acid to the life of storage battery is unfavorable, and with the increase of phosphorus acid content, this trend is more obvious.
So phosphoric acid is added in battery whether need further research to the life-span generation influence of battery as additive.
Organic additive can not only change the property of colloidal electrolyte, can also improve the performance of battery.Commonly use organic add
Plus agent is mainly some high molecular polymers, such as polyacrylamide, polyvinyl alcohol, polyethylene glycol, AEO, paste
Essence, carboxymethyl cellulose etc..The micromolecule additives such as glycerine can improve battery capacity and life-span.Added in colloidal electrolyte
Polyacrylamide and glycerine can absorb colloidal electrolyte because of the excessive moisture that internal structure is shunk and separates out, so as to keep whole
Uniform, the stability of maintenance system of system.The high molecular surfactants such as polyacrylamide, polyvinyl alcohol can be with silicone hydroxyl
Hydrogen bond is formed, the set between silicon dioxide molecules is reduced；In addition, macromolecule volume is larger, silica is spatially hindered
Molecule is approached, and silicon oxygen bond is difficult to be formed, so high molecular surfactant can delay gel process, reduction colloidal electrolyte glues
Property, so as to be easy to encapsulating.Also some organic polymers and complex, such as organic acid, ethers, tartaric acid, EDTA can conducts
Additive is added among electrolyte to improve the charge-discharge performance of battery.
In a word, organic polymer forms adsorption layer in the electrolytic solution, can prevent Pb2+The infiltration of ion, reverts to it
Active metal lead and brown lead oxide, complex can form complex ion with foreign ion therein in the electrolytic solution, so as to reduce
Self discharge, extends the service life of battery.After organic additive is added in right amount, it on the one hand can make gel networks rich in bullet
Property, it on the other hand can also suitably reduce the consumption of gel.So not only it is beneficial to the diffusion mobility of ion and gas, slows down water
Change lamination, and sulfation can be prevented to a certain extent, extend the life-span of gelled lead acid battery.But addition
Agent content is excessive, colloidal electrolyte aquation lamination is occurred.Conversely, additive level is very few, can not be to colloid
Electrolyte and battery produce Beneficial Effect.
Also useful ionic liquid as additives of lead-acid battery report.For example, triethyl group Ammonium hydrogen sulfate, benzyl sulphur
The addition of sour hydrogen amine plasma liquid can increase the utilization rate of positive active material, but add pole plate to a certain extent
The corrosion rate of grid.
In summary, mentioned at present in research both at home and abroad, selection appropriate addn species and additive amount could be made
Colloidal electrolyte of good performance, but there is the difficult control of formula complexity, formula rate, battery performance and improve limited in these researchs
The problem of, meanwhile, it there is no the report for how avoiding that silica gel is settled in battery liquid.
The content of the invention
For the deficiency such as encapsulating in the prior art is difficult, battery performance is unstable, the present invention provides a kind of organo-silicon compound
As application of the additive in colloid storage battery, the organo-silicon compound can improve the viscosity of colloidal electrolyte, extend encapsulating
Time, the internal resistance of cell is reduced, so as to improve the overall performance of colloid storage battery.
Summary of the invention
The organo-silicon compound that the present invention is provided pass through addition as in application process of the additive in colloid storage battery
Effect between agent and silica gel particle, it is to avoid the sedimentation of silica colloid particle, improves the viscosity of colloidal electrolyte, and extension is filled
The glue time；Simultaneously by the special preferred group on such organo-silicon compound, it is formed with the surface of gel particle beneficial to H+Conductive channel, reduce the internal resistance of cell；The good colloid storage battery of performance, the engine applied to vehicle, ship and aircraft can be made
Start, the power supply and emergency standby power of the facility such as the electrical source of power of electric automobile and communication.
Detailed description of the invention
Technical scheme is as follows：
A kind of application of organo-silicon compound as additive in colloid storage battery, the organo-silicon compound have as follows
Structure：
R1-Si(R2R3)R4,
Wherein, R1- Si groups are HO-Si groups or are various groups of the hydrolyzable into HO-Si groups, R4Group is certainly
Body can ionize out the group of Hydrogen Proton or for that can ionize out the group of Hydrogen Proton after hydrolysis；R2、R3Group is not influence this
The various groups of silicone additives self stability.
, according to the invention it is preferred to, the various groups of described hydrolyzable into HO-Si groups are EtO-Si groups, MeO-
Si groups, SiO-Si groups, Cl-Si groups or CH3COO-Si。
, according to the invention it is preferred to, described R4Group be include carboxyl, sulfonic group or phosphonate group various groups or
The various deriveding groups containing above-mentioned three kinds of groups, including-CH can be hydrolyzed to2CH2COOH、-CH2CH2CH2COOH、-
CH2CH2CH2NHCH2CH2COOH、-CH2CH2CH2NHCOCH2CH2COOH、-CH2CH2CH2COOCH3、-CH2CH2CH2COOC
(CH3)3、-CH2CH2COOCH3、-(CH2)10COOCH3、-CH2CH2CH2COOCH2CH3、-CH2CH2CH2NHCOOCH2CH3、-
CH2CH2CH2COONa、-CH2CN、-CH2CH2CH2NCH2CH2CN、-CH2CH2CN、-CH2CH2CH2SO3H、-
CH2CH2CH2NHSO3H、-CH2CH2CH2N(CH2PO3H2)2、-CH2CH2CH2P(O)(OCH2CH3)2、-CH2CH2CH2PO3H2、-
CH2CH2CH2NHC(CH3)2PO3H2、-CH2CH2P(O)(OCH2CH3)2、-CH2CH2CH2NHC(CH3)2P(O)(OCH3CH2)2；It is more excellent
Choosing includes the group of phosphonate group group, most preferably-CH2CH2CH2NHC(CH3)2P(O)(OCH3CH2)2。
, according to the invention it is preferred to, described R2、R3Group is not influence the various of the additive molecule self stability
Group, including methyl, ethyl, phenyl, hydroxyl, alkoxy, polysiloxane group or/and above-mentioned R1、R4Group, more preferably methyl；
R2、R3Group is identical or different.
, according to the invention it is preferred to, described organo-silicon compound have following structure：
HOSi(CH3)2CH2CH2COOH、HOOCCH2CH2CH2Si(CH3)2OSi(CH3)2CH2CH2CH2COOH、HOSi
(CH3)2CH2CH2CH2COOC(CH3)3、(CH3CH2O)3SiCH2CH2COOH、(CH3CH2O)3SiCH2CN、(CH3CH2O)3SiCH2CH2CH2COOH、(CH3CH2O)3SiCH2CH2CN、ClSi(CH3)2CH2CH2CH2CN、Cl2Si(CH3)CH2CH2CN、
(CH3CH2O)3SiCH2CH2COOCH3、(CH3CH2O)3Si(CH2)10COOCH3、(CH3CH2O)3SiCH2CH2CH2NHCOOCH2CH3、
(CH3CH2O)2Si(CH3)CH2CH2P(O)(OCH2CH3)2、(CH3CH2O)3SiCH2CH2CH2NHC(CH3)2P(O)(OCH3CH2)2、
(HO)3SiCH2CH2CH2SO3H、(H2O3PCH2)2NCH2CH2CH2Si(CH3)2OSi(CH3)2CH2CH2CH2N(CH2PO3H2)2Or
(CH3O)3SiCH2CH2P(O)(OCH2CH3)2。
According to the present invention, above-mentioned organo-silicon compound can add as in application process of the additive in colloid storage battery
Being added in sulfuric acid colloidal solution is used for the encapsulating of colloid storage battery, should be added to before silica gel original solution adds sulfuric acid solution
In sulfuric acid solution, concrete application step is as follows：
Silica gel is first dispersed in water at a high speed to the silica gel original solution for being made stable, while the organo-silicon compound are added to
In sulfuric acid solution, mechanical agitation is uniform and controls sulfuric acid solution temperature to be room temperature, silica gel original solution then is added into sulfuric acid molten
In liquid, stirring continues to stir to being all mixed into after homogeneous phase, and colloid storage battery sulfuric acid colloidal solution is made.
Organo-silicon compound of the present invention are conventional products, can also be prepared by prior art, wherein organic
Silicon compound (CH3CH2O)3SiCH2CH2COOH、HOOCCH2CH2CH2Si(CH3)2OSi(CH3)2CH2CH2CH2COOH、HOSi
(CH3)2CH2CH2CH2COOC(CH3)3、Cl2Si(CH3)CH2CH2CN、(CH3CH2O)3Si(CH2)10COOCH3、(CH3CH2O)3SiCH2CH2COOCH3、(CH3CH2O)3SiCH2CH2CN、ClSi(CH3)2CH2CH2CH2CN、(CH3CH2O)3SiCH2CH2CH2NHCOOCH2CH3、(CH3CH2O)2Si(CH3)CH2CH2P(O)(OCH2CH3)2、(CH3CH2O)3SiCH2CH2P(O)
(OCH2CH3)2、(HO)3SiCH2CH2CH2SO3H etc. is on sale in German ABCR companies, the domestic limited public affairs of Shanghai Mai Ruier chemical technologies
There are the agency and sales of these products in Si Dengduo companies；Organo-silicon compound HOSi (CH3)2CH2CH2COOH is in German AKos
Consulting and Solutions GmbH companies are on sale；Organo-silicon compound (H2O3PCH2)2NCH2CH2CH2Si(CH3)2OSi(CH3)2CH2CH2CH2N(CH2PO3H2)2Synthesis can be found in the 17th organosilicon proceeding, page 144~147,
《The synthesis and its research of corrosion inhibition of the new siloxanes containing methylene phosphonic acid groups》；Organo-silicon compound (CH3O)3SiCH2CH2CH2NHC(CH3)2P(O)(OCH3CH2)2Synthesis can be found in Silicon (2011), 3:5-12,《Silica
Naoparticles with Proton Donor and Proton Acceptor Groups:Synthesis and
Aggregation》；Organo-silicon compound (CH3CH2O)3SiCH2CN synthesized reference Wuhan University Journal (natural science edition)
(1998), 44 (6), 717-720,《The catalytic action of the platinum complex of sulfur-bearing nitrogen bidentate ligands organosilicon polymer load》；
Organo-silicon compound (CH3CH2O)3SiCH2CH2CH2NHCOOCH2CH3Synthesized reference PCT Int.Appl. (2014), WO
2014097594 A120140626《Resin Compositions Containing Polyimide Precursors and
Siloxanes Manufacture of Cured Films,and Manufacture of Cured Pattern Films》；
Organo-silicon compound (CH3CH2O)3SiCH2CH2CN synthesis refers to Environmental Science＆Technology
(2013), 47 (15), 8633-8641,《Rapid and Efficient Removal of Microcystins by
Ordered Mesoporous Silica》。
The present invention principle and have the beneficial effect that：
The colloid storage battery of the present invention with organo-silicon compound is macromolecular organo-silicon compound, itself with silicone hydroxyl or
Hydrolysis generation silicone hydroxyl, silicon hydroxyl that can be with silicon dioxide colloid surface by the silicone hydroxyl can occur in an acidic solution for person
Base is bonded, so as to combine closely on silica colloid particle surface, adhesion is strong, battery life further prepared etc.
Long-acting superior performance.The commercially available general colloid storage battery equal non-organic silicon compound of additive, these materials do not contain silicone hydroxyl,
Can not be reacted the stable silica chemistry of silicones key of generation with the silicone hydroxyl of silica surface, therefore and silicon dioxide colloid
The combination force intensity of particle surface is relatively low, thus the long-acting poor performance such as the battery life further prepared.
The colloid storage battery organo-silicon compound of the present invention, containing can ionize out the group of Hydrogen Proton, good hydrophilic property,
Be conducive to additive in an acidic solution and dispersed；After the organo-silicon compound are acted on silica colloid particle,
It can be formed with silica particles beneficial to H+Conductive channel, reduce the internal resistance of cell.In the preparation of colloid storage battery
During, the addition of silicon dioxide colloid can increase solution internal resistance, decline battery performance.Commercially available general colloid storage battery is used
Additive is seldom related to this aspect；For example：Selection uses phosphoric acid, but the use of a large amount of phosphoric acid, influence electrode pad crystal
Structure is formed, battery life has further been harmed on the contrary；Selection uses inorganic salts or organic salt, generally sodium salt, but sodium from
Son is gel catalyst, can accelerate to reunite；Macromolecule organic acid is selected, but is due to that these organic acids are to be simply added, and two
Bond strength between silicon oxide colloid is relatively low, easily departs from during battery use from silica particles, and then
Colloidal electrolyte is set aquation lamination occur.
The colloid storage battery organo-silicon compound of the present invention, are acting on silica particles and are ionizing out hydrogen matter
, can be by the steric hindrance and charge effect of the silicone additives spatial configuration of molecules after son, producing the stagnant power in space prevents two
Silicon oxide colloid condenses, it is to avoid the formation of sedimentation, system is kept collosol state in a long time, is easy to liquid filling to operate；
With additive mostly it is that the purpose is realized by multiple additives collective effect compared to commercially available general colloid storage battery, matches somebody with somebody
Side is complicated, and formula rate is not easily controlled；And the colloid storage battery silicone additives of the present invention, it is one-component, does not deposit
In formula rate control problem, it is easy to industrialized mass production battery.
Focus on siliconated when the colloid storage battery organo-silicon compound of the present invention, its Molecular Design and screening
The stability of compound itself, the characteristics of making it have good stability, resistance to oxidation, it is thus possible to ensure the long-life of battery.It is existing
Have in technology and to be had an effect with silica particles silicone hydroxyl in order to realize and select some high activity groups, these groups
Itself is simultaneously unstable, while also easily reacted with acid solution, thus the long-term use of battery prepared therefrom is stable
Property is not good enough.
The colloid storage battery organo-silicon compound of the present invention, are a kind of silicone macromolecules, containing can ionize out hydrogen
The group of proton, good hydrophilic property, the characteristics of its own has good stability, resistance to oxidation.The silicone additives are water-soluble in sulfuric acid
It can be reacted in liquid with the silicone hydroxyl group of Silica Surface, generate silica silicon key, reduce the excessive silicone hydroxyl of Silica Surface,
So as to improve the viscosity of colloidal electrolyte, extend the encapsulating time；What it was carried simultaneously can ionize out the group of Hydrogen Proton, one
Aspect ensure that the silica gel of organo-silicon compound cladding can be stabilized in sulfuric acid solution, simultaneously as imparting silicon
The property of glue surface negative charge, can be formed with beneficial to H on the surface of gel particle+Conductive channel.The organo-silicon compound
Use, can improve the viscosity of colloidal electrolyte, extend the encapsulating time, reduce the internal resistance of cell.Using such colloid storage battery
With lead-acid accumulator low-temperature characteristics made from organo-silicon compound is good, self discharge is small, long lifespan, and its heavy-current discharge performance
Good, high-multiplying power discharge capacity is big, thus is expected to start applied to the engine of vehicle, ship and aircraft, the power of electric automobile
The power supply and emergency standby power of the facility such as power supply and communication.
Embodiment
Below by specific embodiment, the present invention will be further described, but not limited to this.
It is raw materials used in embodiment to be conventional raw material purchased in market or obtained according to the synthesis of bibliography method.
Embodiment 1
A kind of application of organo-silicon compound as additive in colloid storage battery, the organo-silicon compound have as follows
Structure：
HOSi(CH3)2CH2CH2COOH。
Concrete application step is as follows：
Preparation density is 1.27g/cm3Sulfuric acid solution, according to industry universal formula add typical additives (sodium sulphate
Addition is 1.2%, and the addition of phosphoric acid is 0.12%, and the addition of boric acid is 0.12%, is mass percent), machinery
Stir, and be cooled to room temperature.By above-mentioned organo-silicon compound γ-carboxyl ethylene methyl monohydroxy silane HOSi
(CH3)2CH2CH2COOH is added in sulfuric acid solution (addition of organo-silicon compound is 0.3 g/l), mechanical agitation 5 minutes
And control sulfuric acid solution temperature to be room temperature.Then by silica gel original solution (dioxide-containing silica 23wt%) (sulfuric acid solution in proportion
1/30) volume is added in sulfuric acid solution, and mechanical agitation continues to stir 10 minutes, be made to being all mixed into after homogeneous phase
Colloid storage battery sulfuric acid colloidal solution.
Embodiment 2
As described in Example 1, in concrete application step unlike：Organo-silicon compound γ-carboxyl ethylene methyl
Monohydroxy silane HOSi (CH3)2CH2CH2COOH addition is 1 g/l.
Embodiment 3
As described in Example 1, organosilicon compound species are changed to α, ω-two (carboxyl propylidene) tetramethyl unlike
Disiloxane, structure is as follows：
HOOCCH2CH2CH2Si(CH3)2OSi(CH3)2CH2CH2CH2COOH。
Embodiment 4
As described in Example 1, organosilicon compound species are changed to α, ω-two [(dimethylene-phosphonic acid base amine unlike
Base) propylidene] tetramethyl disiloxane, structure is as follows：
(H2O3PCH2)2NCH2CH2CH2Si(CH3)2OSi(CH3)2CH2CH2CH2N(CH2PO3H2)2。
Embodiment 5
As described in Example 4, in concrete application step unlike：Organo-silicon compound α, ω-two [(dimethylene phosphine
Acidic group amido) propylidene] tetramethyl disiloxane addition be 1 g/l.
Embodiment 6
As described in Example 1, organosilicon compound species are changed to N- (1- diethyl phosphonate bases isopropyl) unlike
Aminopropyl triethoxysilane, structure is as follows：
(MeO)3SiCH2CH2CH2NHC(CH3)2PO(OEt)2。
Embodiment 7
As described in Example 1, organosilicon compound species are changed to itrile group ethylidene chlorodimethyl silane unlike,
Structure is as follows：
ClSi(CH3)2CH2CH2 CH2CN。
Experimental example
The gained colloid storage battery of embodiment 1~7 is subjected to performance test with colloidal solution, as a result as shown in table 1：
The colloid storage battery colloidal solution performance of table 1
| Embodiment project | Solution uniformity coefficient | Solution viscosity | Can the encapsulating time | Settle time of occurrence |
| Embodiment 1 | Uniformly, no layering | Viscosity is low, easily flowing | ＞ 1 day | ＞ 5 days |
| Embodiment 2 | Uniformly, no layering | Viscosity is low, easily flowing | ＞ 2 days | ＞ 10 days |
| Embodiment 3 | Uniformly, no layering | Viscosity is low, easily flowing | ＞ 1 day | ＞ 5 days |
| Embodiment 4 | Uniformly, no layering | Viscosity is low, easily flowing | ＞ 1 day | ＞ 5 days |
| Embodiment 5 | Uniformly, no layering | Viscosity is low, easily flowing | ＞ 2 days | ＞ 10 days |
| Embodiment 6 | Uniformly, no layering | Viscosity is low, easily flowing | ＞ 1 day | ＞ 5 days |
| Embodiment 7 | Uniformly, no layering | Viscosity is low, easily flowing | ＞ 1 day | ＞ 4 days |
The performance test results show that the colloid storage battery colloidal solution prepared using organo-silicon compound of the present invention has
Have that viscosity is low, runny feature, being capable of long-time encapsulating.The time for not occurring settling in not filling colloidal solution is longer.
Show to be formulated for complicated colloid storage battery additive compared to commercially available general using organo-silicon compound of the present invention, work
Sequence is simple, system can be made to keep collosol state in a long time, be easy to liquid filling to operate, as achieve unexpected effect
Really, with very big novelty, it is easy to industrialized mass production battery.
Claims (6)
1. a kind of application of organo-silicon compound as additive in colloid storage battery, it is characterised in that the organosilicon compound
Thing has following structure：
R1-Si(R2R3)R4,
Wherein, R1- Si groups are HO-Si groups or are various groups of the hydrolyzable into HO-Si groups, R4Group is to include
Carboxyl, the group of sulfonic group or phosphonate group and the deriveding group containing carboxyl, sulfonic group or phosphonate group can be hydrolyzed to；R2、R3
Group is not influence the various groups of the silicone additives self stability；
The various groups of described hydrolyzable into HO-Si groups are EtO-Si groups, MeO-Si groups, SiO-Si groups, Cl-Si
Group or CH3COO-Si。
2. application according to claim 1, it is characterised in that described R4Group is-CH2CH2CH2COOH、-
CH2CH2CH2NHCH2CH2COOH、-CH2CH2CH2NHCOCH2CH2COOH、-CH2CH2CH2SO3H、-CH2CH2CH2NHSO3H、-
CH2CH2CH2PO3H2、-CH2CH2CH2NHC(CH3)2PO3H2、-CH2CH2CH2N(CH2PO3H2)2、-CH2CH2CH2COOCH3、-
CH2CH2CN、-CH2CH2CH2NCH2CH2CN、-CH2CH2CH2COOEt、-CH2CH2CH2COONa、-CH2CH2CH2SO3NH2、-
CH2CH2CH2P(O)(OEt)2Or-CH2CH2CH2NHC(CH3)2P(O)(OEt)2。
3. application according to claim 1, it is characterised in that described R2、R3Group be methyl, ethyl, phenyl, hydroxyl,
Alkoxy, polysiloxane group or/and R1、R4Group, R2、R3Group is identical or different.
4. application according to claim 1, it is characterised in that described organo-silicon compound have following structure：
HOSi(CH3)2CH2CH2COOH、HOOCCH2CH2CH2Si(CH3)2OSi(CH3)2CH2CH2CH2COOH、HOSi(CH3)2CH2CH2CH2COOC(CH3)3、(CH3CH2O)3SiCH2CH2COOH、(CH3CH2O)3SiCH2CN、(CH3CH2O)3SiCH2CH2CH2COOH、(CH3CH2O)3SiCH2CH2CN、ClSi(CH3)2CH2CH2CH2CN、Cl2Si(CH3)CH2CH2CN、
(CH3CH2O)3SiCH2CH2COOCH3、(CH3CH2O)3Si(CH2)10COOCH3、(CH3CH2O)3SiCH2CH2CH2NHCOOCH2CH3、
(CH3CH2O)2Si(CH3)CH2CH2P(O)(OCH2CH3)2、(CH3CH2O)3SiCH2CH2CH2NHC(CH3)2P(O)(OCH3CH2)2、
(HO)3SiCH2CH2CH2SO3H、(H2O3PCH2)2NCH2CH2CH2Si(CH3)2OSi(CH3)2CH2CH2CH2N(CH2PO3H2)2Or
(CH3O)3SiCH2CH2P(O)(OCH2CH3)2。
5. application according to claim 1, it is characterised in that organo-silicon compound are added in sulfuric acid colloidal solution and used
In the encapsulating of colloid storage battery.
6. application according to claim 5, it is characterised in that concrete application step is as follows：
Silica gel is first dispersed in water at a high speed to the silica gel original solution for being made stable, while the organo-silicon compound are added into sulfuric acid
In solution, mechanical agitation is uniform and controls sulfuric acid solution temperature to be room temperature, and then silica gel original solution is added in sulfuric acid solution,
Stirring continues to stir to being all mixed into after homogeneous phase, and colloid storage battery sulfuric acid colloidal solution is made.
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| CN105870515B (en) * | 2016-06-08 | 2018-12-28 | 田泽狄 | A kind of silica gel salt surface colloidal electrolyte and preparation method thereof |
| CN106876801B (en) * | 2017-04-05 | 2019-05-14 | 旭派电源有限公司 | A kind of lead-acid accumulator complex colloid electrolyte of chemical crosslinking |
| CN107611488A (en) * | 2017-08-29 | 2018-01-19 | 东莞恒量新能源科技有限公司 | A kind of polymeric additive of lead accumulator and preparation method thereof |
| CN107611490A (en) * | 2017-08-30 | 2018-01-19 | 东莞恒量新能源科技有限公司 | A kind of mixed poly- additive for lead accumulator and preparation method thereof |
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| CN107611491A (en) * | 2017-08-30 | 2018-01-19 | 东莞恒量新能源科技有限公司 | A kind of additive package for lead accumulator and preparation method thereof |
| CN107464959A (en) * | 2017-08-30 | 2017-12-12 | 东莞恒量新能源科技有限公司 | A kind of polymeric additive for lead accumulator and preparation method thereof |
| CN107611496A (en) * | 2017-08-30 | 2018-01-19 | 东莞恒量新能源科技有限公司 | A kind of combined additive for lead accumulator and preparation method thereof |
| CN107394281A (en) * | 2017-08-30 | 2017-11-24 | 东莞恒量新能源科技有限公司 | A kind of additive package of lead storage battery electrolytic solution and preparation method thereof |
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| CN107565173A (en) * | 2017-09-05 | 2018-01-09 | 东莞恒量新能源科技有限公司 | A kind of two-phase polymeric additive of lead accumulator and preparation method thereof |
| CN107611493A (en) * | 2017-09-05 | 2018-01-19 | 东莞恒量新能源科技有限公司 | A kind of two-phase combined additive of lead accumulator and preparation method thereof |
| CN107565174A (en) * | 2017-09-07 | 2018-01-09 | 深圳美能动力科技有限公司 | A kind of two-phase mixtures additive of lead accumulator and preparation method thereof |
| CN107623145A (en) * | 2017-09-13 | 2018-01-23 | 东莞恒量新能源科技有限公司 | A kind of two-phase for lead accumulator mixes poly- additive and preparation method thereof |
| CN107623146A (en) * | 2017-09-13 | 2018-01-23 | 东莞恒量新能源科技有限公司 | A kind of two-phase combined additive, purposes and preparation method thereof |
| CN107611495A (en) * | 2017-09-18 | 2018-01-19 | 东莞恒量新能源科技有限公司 | A kind of two-phase mixture of lead accumulator and preparation method thereof |
| CN107611494A (en) * | 2017-09-18 | 2018-01-19 | 东莞恒量新能源科技有限公司 | A kind of two-phase for lead accumulator mixes polymers additive and preparation method thereof |
| CN107565175A (en) * | 2017-09-18 | 2018-01-09 | 东莞恒量新能源科技有限公司 | A kind of two-phase compositions of lead accumulator and preparation method thereof |
| CN107634270A (en) * | 2017-09-18 | 2018-01-26 | 东莞恒量新能源科技有限公司 | A kind of two-phase for lead accumulator mixes polymers and preparation method thereof |
| CN107579290A (en) * | 2017-09-18 | 2018-01-12 | 东莞恒量新能源科技有限公司 | A kind of two-phase compositions additive, purposes and preparation method thereof |
| CN107579289A (en) * | 2017-09-19 | 2018-01-12 | 深圳美能动力科技有限公司 | A kind of two-phase polymer additive for lead accumulator and preparation method thereof |
| CN114374001B (en) * | 2021-12-31 | 2023-10-27 | 江苏理士电池有限公司 | Novel lead-acid storage battery colloid electrolyte and preparation method thereof |
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| CN1152923C (en) * | 2001-02-23 | 2004-06-09 | 刘粤荣 | Organic high molecular composite for accumulator and its preparation method |
| CN1157442C (en) * | 2001-03-13 | 2004-07-14 | 孙蓉 | 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 |
| CN1663984A (en) * | 2004-03-03 | 2005-09-07 | 天津市润泽化工有限公司 | Modified polysiloxane electrolyte and method for preparing same |
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