CN104538679A - Application of organosilicon compound serving as additive in colloid storage battery - Google Patents

Application of organosilicon compound serving as additive in colloid storage battery Download PDF

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CN104538679A
CN104538679A CN201510018221.6A CN201510018221A CN104538679A CN 104538679 A CN104538679 A CN 104538679A CN 201510018221 A CN201510018221 A CN 201510018221A CN 104538679 A CN104538679 A CN 104538679A
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storage battery
silicon compound
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CN104538679B (en
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卢海峰
乔瑞景
冯圣玉
马厚义
唐波
张悦
廉哲
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Shandong University
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Manufacturing & Machinery (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Silicon Compounds (AREA)

Abstract

The invention relates to the application of organosilicon compound serving as an additive in a colloid storage battery. The organosilicon compound is of the structure of R1-Si (R2R3) R4, wherein the R1-Si group is an HO-Si group or various groups capable of being hydrolyzed into the HO-Si group, the R4 group is a group capable of obtaining hydrogen proton in an ionizing mode by the R4 group or a group capable of obtaining the hydrogen proton in an ionizing mode after being hydrolyzed; the R2 group and R3 group are various groups not affecting the stability of the organosilicon additive. By means of the organosilicon compound, the viscosity of colloid electrolyte can be improved, the glue filling time is prolonged, the internal resistance of the battery is lowered, a manufactured lead-acid battery is good in low-temperature characteristic, low in self discharge, long in service life, good in large-current discharge performance, large in high-rate discharge capacity and expected to be applied to starting of engines of vehicles, ships and airplanes, the power source of electromobiles, communication devices and the like and an emergency power source.

Description

A kind of organo-silicon compound are as the application of additive in colloid storage battery
Technical field
The present invention relates to a kind of organo-silicon compound as the application of additive in colloid storage battery, belong to colloidal battery additive field.
Background technology
Lead acid accumulator refers to that electrode is primarily of plumbous and that oxide is made, electrolyte is sulfuric acid solution a kind of storage battery, has that capacity is large, an advantage of uniformity and good stability, all occupy the first place of chemical power source output all the time.Colloid plumbic storage battery is to one of lead acid accumulator larger innovating reform, have convenient transportation, acid nonleakage, without acid mist, the advantage such as water consumption is slow, natural life-span is long, suppress pole plate corrosion and distortion, prevent active material from coming off, maintenance period is long.Colloid plumbic storage battery not only can be used as the engine start of vehicle, boats and ships, aircraft, also can as the electrical source of power of electric automobile, communications facility power supply, emergency standby power, the accumulation power supply of power plant load equilibrium and the uninterrupted power supply of computer, military applications can also be applied to, the working power of electronic equipment that individual soldier carries, navy submarine, its application constantly expands.The non-maintaining fixed colloid plumbic storage battery of the pregnant solution type grown up in recent years, be post telecommunications system, Electric control operating system, radio system, UPS uninterrupted power supply etc. require the optimal power supply that must not have a power failure in independently-powered or power supply, irreplaceable especially in automotive field, fork truck field, ship domain.
Gelled lead acid battery was begun one's study by American in the twenties in 20th century, within 1966, obtained suitability for industrialized production.The Chinese exploitation lead acid accumulator that begins one's study from the fifties, reached a climax the beginning of the nineties at the end of the eighties.In state-owned part producer adopt traditional silica gel solution preparation colloidal electrolyte, the shortcoming such as can't resolve the layering of colloidal electrolyte aquation all the time, resistance is large, the life-span is short.Therefore, the colloid technology of Chinese independent research need to break through.
In China, electric motor car is a kind of important vehicles, is applicable to the level of consumption of most people, and oil price constantly rises at present, and environmental problem receives much concern, and this be all that the development of the electric motor car cleaned creates chance.Universal along with electric motor car, electric vehicle battery also obtains huge development, and the annual production of China's electric bicycle is more than 2,000 ten thousand, and the annual production of battery of electric bicycle is close to 4,000 ten thousand thousand volt-ampere hours.Battery is one of electric motor car core component.Performances of the lead-acid battery is reliable and stable, technology maturation, low price, cost performance are higher, shows one's talent from various chemical power source, becomes the main force of battery of electric vehicle.But the problems such as lead-acid battery exists, and self-discharge rate is large, electrolyte stratification, sulfation, thermal runaway, deep discharge cycle performance difference, do not reach expectation and the requirement of consumer.In order to improve battery of electric vehicle performance, people attempt colloidal electrolyte technology to refer to battery of electric vehicle, but a lot of enterprise just adds the silicon dioxide of about 0.6wt% in the electrolyte of battery of electric vehicle at present, and battery performance slightly improves, but effect is still undesirable.Obtain the gel battery for electric vehicle of excellent performance, still need to carry out a large amount of research work.
Use colloidal electrolyte to be current mainstream development direction in analysing valve control type lead-acid accumulator battery, it can overcome leakage, acid solution layering that battery exists effectively, deeper cavity electric discharge is lower uses not good shortcoming.Colloidal electrolyte is the key factor affecting gelled lead acid battery capacity and cycle life.Wherein gel, the volume fraction of joining glue sulfuric acid and additive etc. all have impact to the performance of colloidal electrolyte.
Aerosil is electrolyte gelling agent conventional in the world at present, uses its obtained gelled lead acid battery function admirable.Johnson company of the U.S., German Hagen company and Japanese GS company all use aerosil to prepare colloidal electrolyte of lead acid accumulator.Aerosil particle surface is rich in hydroxyl, in aqueous sulfuric acid, easily form three-dimensional netted gel structure by hydrogen bond action.Even if but be only preliminary gelatification, the viscosity of electrolyte also can sharply raise, and causes being difficult to pour in the battery of compact texture, and the problem of encapsulating difficulty becomes restriction and advances one of Main Bottleneck of colloidal electrolyte application.Find in actual silica gel storage battery production process, do not carry out filling colloidal electrolyte in put procedure, precipitation can be formed because of the reunion between silica colloid particle, make electrolyte overall distribution uneven, and then cause the reduction of battery performance.If there is no special viscosity modifier, deflocculant and other additives, be the performance and the quality that are difficult to control silica-gel accumulator.
With high-molecular organic material, modification carried out to silicon dioxide microparticle and make colloidal electrolyte, have been reported in current disclosed technical literature or patent document, such as, Chinese patent document CN1663984A (application number: 200410018708.6) disclose a kind of modified polyorganosiloxane electrolyte and preparation method thereof, containing multiple modified polyorganosiloxane, also comprise tetraethoxysilane, positive silicic acid propyl ester or butyl silicate; Water-soluble polypropylene acid; High-purity sulphuric acid and industrial pure water.Polyether segment imparts the water-soluble and hydrophily of colloid, plays emulsification, and can have good wetting action with battery lead plate.With carboxyl in carbon functional silicone structure, they can be formed on the surface of gel particle and be beneficial to H +conductive channel.The lead acid accumulator low-temperature characteristics obtained with this kind of colloidal electrolyte is good, self discharge is little, the life-span is long, have outstanding electric recovery capability, and its good heavy current, the general lead acid accumulator of high-multiplying power discharge Capacity Ratio large more than 30%.
But preparation thixotropy colloidal electrolyte that is good, electrochemical performance also needs the support of various additive.Use suitable additive can improve the viscosity of colloidal electrolyte, improve process for filling colloid into, reduce the internal resistance of cell.The colloidal electrolyte of colloid electrode due to viscosity comparatively large, the active material above electrode is hindered in the process of transmission, causes polar board surface easily to form PbSO 4precipitation, makes battery capacity reduce, ultimate failure, and this also makes the capacity of colloid battery will lower than AGM battery.Colloid battery easily causes battery float unbalanced in charging process, and colloidal electrolyte is easier to occur aquation lamination in charge and discharge process, and solid-liquid there will be obvious interface, makes battery failure.Additive is added in colloidal electrolyte, have do not change battery industry production process, fringe cost low, effective, be convenient to the advantages such as popularization, all actively develop additive agent electrolyte miscellaneous both at home and abroad at present, select suitable additive agent electrolyte to be the main path improving colloid battery performance.
Adding of gel additives, the surface state of gelinite can be changed, when gel particles is close to each other, due to the steric restriction of its macromolecular chain, must hinder interparticle close further, make to be difficult between particle react, silicon oxygen bond is difficult to be formed, and has retarding action to the colloid condense process of gelinite.Conventional gel additives comprises the kinds such as inorganic additive, organic additive and ionic liquid.
Conventional inorganic additive has sulfate, phosphoric acid and boric acid etc.Have bibliographical information, phosphoric acid can improve the structure of grid corrosion layer, increases the adhesion of active material and grid, and weaving active material comes off; Phosphoric acid can also reduce the formation of lead sulfate passivation layer, is beneficial to acid and diffuses into the participation reaction of pole plate inside.Meissner thinks, the forming process that phosphoric acid can affect lead sulfate crystal in battery is added in electrolyte, make lead sulfate crystal more tiny, make the long-pending increase of the real surface of electrode, reduce polarization of electrode degree in charge/discharge process, thus reduce the precipitation rate of oxygen on electrode, reduce the fluid loss of battery, thus can reduce battery causes inefficacy possibility because of electrolyte dry-out.What Vinod thought appropriate phosphoric acid adds the corrosion resistance that can increase positive active material and grid alloy interface, thus improves the deeper cavity life-span of battery.But also have bibliographical information, phosphoric acid to add the impact of the life of storage battery be disadvantageous, and along with the increase of phosphorus acid content, this trend is more obvious.So whether phosphoric acid joins in storage battery to have an impact to the life-span of battery as additive need further research.
Organic additive not only can change the character of colloidal electrolyte, also can improve the performance of battery.Conventional organic additive is some high molecular polymers mainly, as polyacrylamide, polyvinyl alcohol, polyethylene glycol, AEO, dextrin, carboxymethyl cellulose etc.The micromolecule additives such as glycerine can improve battery capacity and life-span.In colloidal electrolyte, add polyacrylamide and glycerine can absorb the excessive moisture that colloidal electrolyte separates out because internal structure is shunk, thus keep the even of whole system, the stability of maintenance system.The high molecular surfactant such as polyacrylamide, polyvinyl alcohol can form hydrogen bond with silicone hydroxyl, reduces the set between silicon dioxide molecules; In addition, macromolecule volume is comparatively large, spatially hinders silicon dioxide molecules close, and silicon oxygen bond is difficult to be formed, so high molecular surfactant can delay gel process, reduces colloidal electrolyte viscosity, thus is easy to encapsulating.Also have some organic polymers and complex, as organic acid, ethers, tartaric acid, EDTA etc., can be used as additive and be added in the middle of electrolyte to improve the charge-discharge performance of battery.
In a word, organic polymer forms adsorption layer in the electrolytic solution, can stop Pb 2+the infiltration of ion, makes it revert to active metal lead and brown lead oxide, and complex can form complex ion with foreign ion wherein in the electrolytic solution, thus reduces self discharge, extends the useful life of battery.After organic additive adds in right amount, gel networks high resilience can be made on the one hand, also suitably can reduce the consumption of gel on the other hand.So not only be beneficial to the diffusion mobility of ion and gas, slow down aquation lamination, and can sulfation be stoped to a certain extent, extend the life-span of gelled lead acid battery.But additive level is excessive, colloidal electrolyte is easily made to occur aquation lamination.Otherwise additive level is very few, Beneficial Effect can not be produced to colloidal electrolyte and storage battery.
Also useful ionic liquid is as the report of additives of lead-acid battery.Such as, triethyl group Ammonium hydrogen sulfate, benzyl Ammonium hydrogen sulfate plasma liquid add the utilance that can increase positive active material, but add the corrosion rate of electrode plate grid to a certain extent.
In sum, mention in research both at home and abroad at present, select appropriate addn kind and additive amount could obtain colloidal electrolyte of good performance, but these research existence formula complexity, the difficult control of formula rate, battery performance improve limited problem, meanwhile, there is no the report how avoiding silica gel sedimentation in battery liquid.
Summary of the invention
For deficiencies such as encapsulating in prior art are difficult, battery performance is unstable, the invention provides a kind of organo-silicon compound as the application of additive in colloid storage battery, these organo-silicon compound can improve the viscosity of colloidal electrolyte, extend the encapsulating time, reduce the internal resistance of cell, thus improve the overall performance of colloid storage battery.
Summary of the invention
Organo-silicon compound provided by the invention, as in the application process of additive in colloid storage battery, by the effect between additive and silica gel particle, are avoided the sedimentation of silica colloid particle, are improved the viscosity of colloidal electrolyte, extend the encapsulating time; Simultaneously by the special preferred group on such organo-silicon compound, be formed on the surface of gel particle and be beneficial to H +conductive channel, reduce the internal resistance of cell; The good colloid storage battery of performance can be obtained, be applied to the engine start of vehicle, boats and ships and aircraft, the electrical source of power of electric automobile and the power supply of facilities such as communicating and emergency standby power.
Detailed Description Of The Invention
Technical scheme of the present invention is as follows:
Organo-silicon compound are as the application of additive in colloid storage battery, and these organo-silicon compound have following structure:
R 1-Si(R 2R 3)R 4，
Wherein, R 1-Si group is HO-Si group or becomes the various groups of HO-Si group, R for hydrolyzable 4group is self to ionize out the group of Hydrogen Proton or the group for ionizing out Hydrogen Proton after hydrolysis; R 2, R 3group is the various groups not affecting this silicone additives self stability.
According to the present invention, preferably, described hydrolyzable becomes the various groups of HO-Si group to be EtO-Si group, MeO-Si group, SiO-Si group, Cl-Si group or CH 3cOO-Si.
According to the present invention, preferably, described R 4group is the various deriveding groups that the various groups including carboxyl, sulfonic group or phosphonate group maybe can be hydrolyzed to containing above-mentioned three kinds of groups, comprises-CH 2cH 2cOOH ,-CH 2cH 2cH 2cOOH ,-CH 2cH 2cH 2nHCH 2cH 2cOOH ,-CH 2cH 2cH 2nHCOCH 2cH 2cOOH ,-CH 2cH 2cH 2cOOCH 3,-CH 2cH 2cH 2cOOC (CH 3) 3,-CH 2cH 2cOOCH 3,-(CH 2) 10cOOCH 3,-CH 2cH 2cH 2cOOCH 2cH 3,-CH 2cH 2cH 2nHCOOCH 2cH 3,-CH 2cH 2cH 2cOONa ,-CH 2cN ,-CH 2cH 2cH 2nCH 2cH 2cN ,-CH 2cH 2cN ,-CH 2cH 2cH 2sO 3h ,-CH 2cH 2cH 2nHSO 3h ,-CH 2cH 2cH 2n (CH 2pO 3h 2) 2,-CH 2cH 2cH 2p (O) (OCH 2cH 3) 2,-CH 2cH 2cH 2pO 3h 2,-CH 2cH 2cH 2nHC (CH 3) 2pO 3h 2,-CH 2cH 2p (O) (OCH 2cH 3) 2,-CH 2cH 2cH 2nHC (CH 3) 2p (O) (OCH 3cH 2) 2; More preferably the group of phosphonate group group is comprised, most preferably-CH 2cH 2cH 2nHC (CH 3) 2p (O) (OCH 3cH 2) 2.
According to the present invention, preferably, described R 2, R 3group is the various groups not affecting this additive molecule self stability, comprises methyl, ethyl, phenyl, hydroxyl, alkoxyl, polysiloxane group or/and above-mentioned R 1, R 4group, more preferably methyl; R 2, R 3group is identical or different.
According to the present invention, preferably, described organo-silicon compound have following structure:
HOSi (CH 3) 2cH 2cH 2cOOH, HOOCCH 2cH 2cH 2si (CH 3) 2oSi (CH 3) 2cH 2cH 2cH 2cOOH, HOSi (CH 3) 2cH 2cH 2cH 2cOOC (CH 3) 3, (CH 3cH 2o) 3siCH 2cH 2cOOH, (CH 3cH 2o) 3siCH 2cN, (CH 3cH 2o) 3siCH 2cH 2cH 2cOOH, (CH 3cH 2o) 3siCH 2cH 2cN, ClSi (CH 3) 2cH 2cH 2cH 2cN, Cl 2si (CH 3) CH 2cH 2cN, (CH 3cH 2o) 3siCH 2cH 2cOOCH 3, (CH 3cH 2o) 3si (CH 2) 10cOOCH 3, (CH 3cH 2o) 3siCH 2cH 2cH 2nHCOOCH 2cH 3, (CH 3cH 2o) 2si (CH 3) CH 2cH 2p (O) (OCH 2cH 3) 2, (CH 3cH 2o) 3siCH 2cH 2cH 2nHC (CH 3) 2p (O) (OCH 3cH 2) 2, (HO) 3siCH 2cH 2cH 2sO 3h, (H 2o 3pCH 2) 2nCH 2cH 2cH 2si (CH 3) 2oSi (CH 3) 2cH 2cH 2cH 2n (CH 2pO 3h 2) 2or (CH 3o) 3siCH 2cH 2p (O) (OCH 2cH 3) 2.
According to the present invention, above-mentioned organo-silicon compound are as in the application process of additive in colloid storage battery, can add the encapsulating for colloid storage battery in sulfuric acid colloidal solution to, should join in sulfuric acid solution before silica gel original solution adds sulfuric acid solution, embody rule step be as follows:
First silica gel high speed dispersion is obtained stable silica gel original solution in water, these organo-silicon compound are joined in sulfuric acid solution simultaneously, mechanical agitation evenly and to control sulfuric acid solution temperature be room temperature, subsequently silica gel original solution is joined in sulfuric acid solution, be stirred to after being all mixed into homogeneous phase, continue to stir, obtained colloid storage battery sulfuric acid colloidal solution.
Organo-silicon compound of the present invention are conventional products, also can prepare by prior art, wherein organo-silicon compound (CH 3cH 2o) 3siCH 2cH 2cOOH, HOOCCH 2cH 2cH 2si (CH 3) 2oSi (CH 3) 2cH 2cH 2cH 2cOOH, HOSi (CH 3) 2cH 2cH 2cH 2cOOC (CH 3) 3, Cl 2si (CH 3) CH 2cH 2cN, (CH 3cH 2o) 3si (CH 2) 10cOOCH 3, (CH 3cH 2o) 3siCH 2cH 2cOOCH 3, (CH 3cH 2o) 3siCH 2cH 2cN, ClSi (CH 3) 2cH 2cH 2cH 2cN, (CH 3cH 2o) 3siCH 2cH 2cH 2nHCOOCH 2cH 3, (CH 3cH 2o) 2si (CH 3) CH 2cH 2p (O) (OCH 2cH 3) 2, (CH 3cH 2o) 3siCH 2cH 2p (O) (OCH 2cH 3) 2, (HO) 3siCH 2cH 2cH 2sO 3h etc. are on sale in German ABCR company, and all there are the agency and sales of these products in domestic Shanghai Deng Duo company of Mai Ruier chemical technology Co., Ltd; Organo-silicon compound HOSi (CH 3) 2cH 2cH 2cOOH is on sale in German AKos Consulting and Solutions GmbH company; Organo-silicon compound (H 2o 3pCH 2) 2nCH 2cH 2cH 2si (CH 3) 2oSi (CH 3) 2cH 2cH 2cH 2n (CH 2pO 3h 2) 2synthesis can see the 17 organosilicon proceeding, 144 ~ 147 pages, " novel containing the synthesis of methylene phosphonic acid groups siloxanes and the research of corrosion inhibition thereof "; Organo-silicon compound (CH 3o) 3siCH 2cH 2cH 2nHC (CH 3) 2p (O) (OCH 3cH 2) 2synthesis can see Silicon (2011), 3:5-12, " Silica Naoparticles with Proton Donor and Proton Acceptor Groups:Synthesis and Aggregation "; Organo-silicon compound (CH 3cH 2o) 3siCH 2synthesized reference Wuhan University Journal (natural science edition) (1998) of CN, 44 (6), 717-720, " catalytic action of the platinum complex of sulfur-bearing nitrogen bidentate ligands organosilicon polymer load "; Organo-silicon compound (CH 3cH 2o) 3siCH 2cH 2cH 2nHCOOCH 2cH 3synthesized reference PCT Int.Appl. (2014), WO 2014097594 A120140626 " Resin Compositions Containing PolyimidePrecursors and Siloxanes Manufacture of Cured Films, and Manufacture of Cured Pattern Films "; Organo-silicon compound (CH 3cH 2o) 3siCH 2cH 2the synthesis of CN can with reference to Environmental Science & Technology (2013), 47 (15), 8633-8641, " Rapid and Efficient Removal of Microcystins byOrdered Mesoporous Silica ".
Principle of the present invention and beneficial effect as follows:
Colloid storage battery organo-silicon compound of the present invention are large molecule organo-silicon compound, self is with silicone hydroxyl or hydrolysis generation silicone hydroxyl can occur in an acidic solution, by this silicone hydroxyl can with the silicone hydroxyl generation bonding of dioxide/silica gel surface, thus combine closely on silica colloid particle surface, the long-lasting energy such as adhesion is strong, the battery life of preparation are further superior.The equal non-organic silicon compound of commercially available all-purpose gum accumulator body additive, these materials are not containing silicone hydroxyl, can not react with the silicone hydroxyl of silica surface and generate stable silica chemistry of silicones key, therefore lower with the adhesion intensity on silica colloid particle surface, the long-lasting energy such as the battery life of thus preparation are further not good enough.
Colloid storage battery organo-silicon compound of the present invention, containing ionizing out the group of Hydrogen Proton, good hydrophilic property, are conducive to additive in an acidic solution and dispersed; After these organo-silicon compound and silica colloid particle effect, can be formed at silica particles and be beneficial to H +conductive channel, reduce the internal resistance of cell.In the preparation process of colloid storage battery, the membership that adds of silicon dioxide colloid increases solution internal resistance, and battery performance is declined.Commercially available general colloid storage battery additive seldom relates to this aspect; Such as: choice for use phosphoric acid, but the use of a large amount of phosphoric acid, affect the formation structure of electrode pad crystal, harm battery life further on the contrary; Choice for use inorganic salts or organic salt, be generally sodium salt, but sodium ion is gel catalyst, can accelerate to reunite; Select macromolecule organic acid, but due to these organic acids be simply add, and bond strength between silicon dioxide colloid is lower, easily departs from from silica particles in battery use procedure, and then makes colloidal electrolyte occur aquation lamination.
Colloid storage battery organo-silicon compound of the present invention, with silica particles effect and after ionizing out Hydrogen Proton, can by the steric hindrance of this silicone additives spatial configuration of molecules and charge effect, producing the stagnant power in space prevents silicon dioxide colloid from condensing, avoid the formation of sedimentation, make system keep collosol state in a long time, be convenient to fill with liquid operation; Be mostly realize this object by multiple additives acting in conjunction compared to commercially available general colloid storage battery additive, formula is complicated, and formula rate is not easy to control; And colloid storage battery silicone additives of the present invention, be one-component, there is not formula rate control problem, be convenient to industrialized mass production storage battery.
Colloid storage battery organo-silicon compound of the present invention, have focused on the stability of organo-silicon compound self, have made it have good stability, sludge proof feature, thus can ensure the long-life of storage battery when its Molecular Design and screening.Some high activity groups are selected in order to realize having an effect with silica particles silicone hydroxyl in prior art, these groups self are also unstable, also easy and acid solution reacts simultaneously, and thus the Long-Time Service stability of storage battery prepared therefrom is not good enough.
Colloid storage battery organo-silicon compound of the present invention are a kind of silicone macromolecules, and containing the group that can ionize out Hydrogen Proton, good hydrophilic property, himself has good stability, sludge proof feature.This silicone additives can react with the silicone hydroxyl group of Silica Surface in aqueous sulfuric acid, generates silica silicon key, reduces the silicone hydroxyl that Silica Surface is too much, thus improve the viscosity of colloidal electrolyte, extend the encapsulating time; Simultaneously its with the group that can ionize out Hydrogen Proton, ensure that on the one hand the coated silica gel of these organo-silicon compound can in sulfuric acid solution stable existence, meanwhile, owing to imparting the character of Silica Surface negative electrical charge, can be formed on the surface of gel particle and be beneficial to H +conductive channel.The use of these organo-silicon compound, can improve the viscosity of colloidal electrolyte, extends the encapsulating time, reduces the internal resistance of cell.The lead acid accumulator low-temperature characteristics adopting such colloid storage battery organo-silicon compound obtained is good, self discharge is little, the life-span is long, and its good heavy current, high-multiplying power discharge capacity is large, thus the engine start being applied to vehicle, boats and ships and aircraft is expected to, the electrical source of power of electric automobile and the power supply of facilities such as communicating and emergency standby power.
Embodiment
Below by specific embodiment, the present invention will be further described, but be not limited thereto.
In embodiment raw materials used be conventional commercial raw material or according to list of references method synthesis obtain.
Embodiment 1
Organo-silicon compound are as the application of additive in colloid storage battery, and these organo-silicon compound have following structure:
HOSi(CH 3) 2CH 2CH 2COOH。
Embody rule step is as follows:
Preparation density is 1.27g/cm 3sulfuric acid solution, add typical additives (addition of sodium sulphate is 1.2%, and the addition of phosphoric acid is 0.12%, and the addition of boric acid is 0.12%, is mass percent) according to industry universal formula, mechanical agitation is even, and is cooled to room temperature.By above-mentioned organo-silicon compound γ-carboxyl ethylene methyl monohydroxy silane HOSi (CH 3) 2cH 2cH 2cOOH joins (addition of organo-silicon compound is 0.3 grams per liter) in sulfuric acid solution, mechanical agitation 5 minutes to control sulfuric acid solution temperature be room temperature.Then by silica gel original solution (dioxide-containing silica 23wt%) in proportion (1/30 of sulfuric acid solution volume) join in sulfuric acid solution, after mechanical agitation is extremely all mixed into homogeneous phase, continue stirring 10 minutes, obtained colloid storage battery sulfuric acid colloidal solution.
Embodiment 2
As described in Example 1, unlike in embody rule step: organo-silicon compound γ-carboxyl ethylene methyl monohydroxy silane HOSi (CH 3) 2cH 2cH 2the addition of COOH is 1 grams per liter.
Embodiment 3
As described in Example 1, change α into unlike by organosilicon compound species, ω-two (carboxyl propylidene) tetramethyl disiloxane, structure is as follows:
HOOCCH 2CH 2CH 2Si(CH 3) 2OSi(CH 3) 2CH 2CH 2CH 2COOH。
Embodiment 4
As described in Example 1, change α into unlike by organosilicon compound species, ω-two [(dimethylene-phosphonic acid base amido) propylidene] tetramethyl disiloxane, structure is as follows:
(H 2O 3PCH 2) 2NCH 2CH 2CH 2Si(CH 3) 2OSi(CH 3) 2CH 2CH 2CH 2N(CH 2PO 3H 2) 2。
Embodiment 5
As described in Example 4, unlike in embody rule step: the addition of organo-silicon compound α, ω-two [(dimethylene-phosphonic acid base amido) propylidene] tetramethyl disiloxane is 1 grams per liter.
Embodiment 6
As described in Example 1, unlike organosilicon compound species being changed into N-(1-diethyl phosphonate base isopropyl) aminopropyl triethoxysilane, structure is as follows:
(MeO) 3SiCH 2CH 2CH 2NHC(CH 3) 2PO(OEt) 2。
Embodiment 7
As described in Example 1, change itrile group ethylidene chlorodimethyl silane into unlike by organosilicon compound species, structure is as follows:
ClSi(CH 3) 2CH 2CH 2CH 2CN。
Experimental example
Embodiment 1 ~ 7 gained colloid storage battery colloidal solution is carried out performance test, and result is as shown in table 1:
Table 1 colloid storage battery colloidal solution performance
Embodiment project Dissolution homogeneity degree Solution viscosity Can the encapsulating time Sedimentation time of occurrence
Embodiment 1 Evenly, without layering Viscosity is low, easily flows > 1 day > 5 days
Embodiment 2 Evenly, without layering Viscosity is low, easily flows > 2 days > 10 days
Embodiment 3 Evenly, without layering Viscosity is low, easily flows > 1 day > 5 days
Embodiment 4 Evenly, without layering Viscosity is low, easily flows > 1 day > 5 days
Embodiment 5 Evenly, without layering Viscosity is low, easily flows > 2 days > 10 days
Embodiment 6 Evenly, without layering Viscosity is low, easily flows > 1 day > 5 days
Embodiment 7 Evenly, without layering Viscosity is low, easily flows > 1 day > 4 days
The performance test results shows, applies colloid storage battery colloidal solution prepared by organo-silicon compound of the present invention, has low, the runny feature of viscosity, can encapsulating for a long time.Do not occur in not filling colloidal solution that the time of sedimentation is longer.Show the colloid storage battery additive adopting organo-silicon compound of the present invention compared to commercially available general formula complexity, operation is simple, system can be made to keep collosol state in a long time, be convenient to fill with liquid operation, be and achieve beyond thought effect, there is very large novelty, be convenient to industrialized mass production storage battery.

Claims (8)

1. organo-silicon compound are as the application of additive in colloid storage battery, it is characterized in that, these organo-silicon compound have following structure: R 1-Si (R 2r 3) R 4,
Wherein, R 1-Si group is HO-Si group or becomes the various groups of HO-Si group, R for hydrolyzable 4group is self to ionize out the group of Hydrogen Proton or the group for ionizing out Hydrogen Proton after hydrolysis; R 2, R 3group is the various groups not affecting this silicone additives self stability.
2. application according to claim 1, is characterized in that, described hydrolyzable becomes the various groups of HO-Si group to be EtO-Si group, MeO-Si group, SiO-Si group, Cl-Si group or CH 3cOO-Si.
3. application according to claim 1, is characterized in that, described R 4group is the group including carboxyl, sulfonic group or phosphonate group and the deriveding group that can be hydrolyzed to containing carboxyl, sulfonic group or phosphonate group.
4. application according to claim 3, is characterized in that, described R 4group is-CH 2cH 2cH 2cOOH ,-CH 2cH 2cH 2nHCH 2cH 2cOOH ,-CH 2cH 2cH 2nHCOCH 2cH 2cOOH ,-CH 2cH 2cH 2sO 3h ,-CH 2cH 2cH 2nHSO 3h ,-CH 2cH 2cH 2pO 3h 2,-CH 2cH 2cH 2nHC (CH 3) 2pO 3h 2,-CH 2cH 2cH 2n (CH 2pO 3h 2) 2,-CH 2cH 2cH 2cOOCH 3,-CH 2cH 2cN ,-CH 2cH 2cH 2nCH 2cH 2cN ,-CH 2cH 2cH 2cOOEt ,-CH 2cH 2cH 2cOONa ,-CH 2cH 2cH 2sO 3nH 2,-CH 2cH 2cH 2p (O) (OEt) 2or-CH 2cH 2cH 2nHC (CH 3) 2p (O) (OEt) 2.
5. application according to claim 1, is characterized in that, described R 2, R 3group is that methyl, ethyl, phenyl, hydroxyl, alkoxyl, polysiloxane group are or/and R 1, R 4group, R 2, R 3group is identical or different.
6. application according to claim 1, is characterized in that, described organo-silicon compound have following structure:
HOSi (CH 3) 2cH 2cH 2cOOH, HOOCCH 2cH 2cH 2si (CH 3) 2oSi (CH 3) 2cH 2cH 2cH 2cOOH, HOSi (CH 3) 2cH 2cH 2cH 2cOOC (CH 3) 3, (CH 3cH 2o) 3siCH 2cH 2cOOH, (CH 3cH 2o) 3siCH 2cN, (CH 3cH 2o) 3siCH 2cH 2cH 2cOOH, (CH 3cH 2o) 3siCH 2cH 2cN, ClSi (CH 3) 2cH 2cH 2cH 2cN, Cl 2si (CH 3) CH 2cH 2cN, (CH 3cH 2o) 3siCH 2cH 2cOOCH 3, (CH 3cH 2o) 3si (CH 2) 10cOOCH 3, (CH 3cH 2o) 3siCH 2cH 2cH 2nHCOOCH 2cH 3, (CH 3cH 2o) 2si (CH 3) CH 2cH 2p (O) (OCH 2cH 3) 2, (CH 3cH 2o) 3siCH 2cH 2cH 2nHC (CH 3) 2p (O) (OCH 3cH 2) 2, (HO) 3siCH 2cH 2cH 2sO 3h, (H 2o 3pCH 2) 2nCH 2cH 2cH 2si (CH 3) 2oSi (CH 3) 2cH 2cH 2cH 2n (CH 2pO 3h 2) 2or (CH 3o) 3siCH 2cH 2p (O) (OCH 2cH 3) 2.
7. application according to claim 1, is characterized in that, organo-silicon compound is added to the encapsulating being used for colloid storage battery in sulfuric acid colloidal solution.
8. application according to claim 7, is characterized in that, embody rule step is as follows:
First silica gel high speed dispersion is obtained stable silica gel original solution in water, these organo-silicon compound are joined in sulfuric acid solution simultaneously, mechanical agitation evenly and to control sulfuric acid solution temperature be room temperature, subsequently silica gel original solution is joined in sulfuric acid solution, be stirred to after being all mixed into homogeneous phase, continue to stir, obtained colloid storage battery sulfuric acid colloidal solution.
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